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I75l"'5-'^'^ OCT IV 1975

NBS SPECIAL PUBLICATION 409

U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards

Marine Polluiioh Monitoring

(Petroleum)

Proceedings of a Symposium Sponsored by

The Intergovernmental The World Meteorological

Oceanographic Commission Organization

(lOC-UNESCO) (WMG)

United States

Department

of Commerce
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards' was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology

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" Part of the Center for Radiation Research.

3 Located at Boulder, Colorado 80302.

Part of the Center for Building Technology.
Marine Pollution Monitoring (Petroleum)

Proceedings of a Symposium and Workshop

Held at the National Bureau of Standards,

Gaithersburg, Md., May 13-17, 1974

Sponsored by

The Intergovernmental Oceanographic

Commission (IOC-UNESCO)

The World Meteorological Organization

The U.S. Department of Commerce

R. C. Junghans, Conference Coordinator

National Oceanic Atmospheric Administration (NOAA)

6010 Executive Boulevard, Rockville, Maryland 20852

U.S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretory

(j»S, NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

*i

Issued December 1974
Library of Congress Cataloging in Publication Data

Marine Pollution Monitoring (Petroleum) Symposium and

Workshop, National Bureau of Standards, 197^.

Marine pollution monitoring (petroleum)

(KBS special publication ; ^09)

Includes index.

Supt. of Docs, no.: C 13.10:^+09

1. Oil pollution of river, harbors, etc. --Congresses.

2. Oil spills and mldlife--Congresses. I. Intergovernmental Oceanographic Commission. II. World Meteorological Organizationo III. United States. Dept. of

Commerce. IV. Title. V. Series: United States.

National Bureau of Standards. Special publication ; hO^.

Q,C100.U57 no. k09 [GCIO80] 389'o08s [628.1'683]

7^-311^2

National Bureau of Standards Special Publication 409

Nat. Bur. Stand. (U.S.), Spec. Publ. 409, 293 pages (Dec. 1974) CODEN: XNBSAV

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1974

For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 Price $3.90 Stock Number 0303-01359
ABSTRACT

These proceedings contain the invited plenary lectures representing

pertinent scientific, environmental, and regulatory aspects of petroleum

hydrocarbon measurements, the summaries of the contributed papers, dealing with specific scientific developments and recommendations, and the

recommendations of the topical discussion groups. Also included is a report of an international workshop which provides specific recommendations for the initiation of a coordinated Pilot Project for marine

pollution (petroleum) monitoring.

Key Words: Analytical methods; data reporting procedures; Intergovernmental Oceanographic Commission (IOC); marine pollution

(petroleum) monitoring; Maritime Administration (MarAd)

;

National Bureau of Standards (NBS) ; National Oceanic and

Atmospheric Administration (NOAA) ; petroleum hydrocarbon

measurement; oil slicks and tar balls; sampling methods;

World Meterological Organization (WMO)

.

ill
1
FOREWORD

The increasing amount of petroleum being transported over the

world's waterways has prompted a good deal of interest in the environmental impact of oil pollution. The need for a comprehensive international marine environmental monitoring assessment program serving

both research and operational activities is recognized by the U. S.

Department of Commerce. Thus it was proper that three agencies within

the Department of Commerce, the Maritime Administration (MarAd) , the

National Bureau of Standards (NBS) , and the National Oceanic and Atmospheric Administration (NOAA) cosponsor and host the Marine Pollution

Monitoring (Petroleum) Symposiumjand Workshop held at NBS in Gaithersburg,

May 13-17, 1974.

The publication of the proceedings of this meeting is the joint

eff ort of MarAd, NBS and NOAA. This book contains the invited plenary

lectures, the summaries of the contributed papers and the recommendations of the topical discussion groups as well as the Workshop's

recommended procedures and methodology for use by National Coordinators in the implementation, at the national level, of the operational

programs for the Pilot Project on Marine Pollution Monitoring.

J. D. Hoffman, Director

Institute for Materials Research

National Bureau of Standards

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vi
PREFACE

The International Sjnnposium and Workshop was prompted by the recognized

need to conmunicate and exchange ideas and results on an international basis

,

which reflect the status of current methodology for making measurements of

petroleum and petroleum products in the marine environment. Such needs arose

as the Intergovernmental Oceanographic Commission and the World Meteorological

Organization decided to establish an operational Pilot Project for Marine

Pollution Monitoring which was initially to focus on petroleum hydrocarbons

within the framework of the IGOSS program.

IGOSS , the Integrated Global Ocean Station System, is aimed at evolving a comprehensive international marine environmental monitoring, assessment and

prediction program of services to various categories of ocean users—both for

research support and for operational activities.

The objective of the Pilot Project on Marine Pollution Monitoring is to

initiate and expand an internationally coordinated program for marine pollution

monitoring, initially in selected ocean areas, in order to acquire and exchange

among nations intercomparable data for making assessments of the periodic state

and degrees of contamination of the marine environment; and, to establish the

organizational machinery required for further development and expansion of

marine pollution monitoring.

The objectives of the Workshop were: (a) to provide scientific and

technical advice, based mainly on information supplied by the Symposium, as to

the methodology (observation and reporting, sampling, sample preservation,

analysis, standards criteria, data handling) to be used or initiated during

the Pilot Project, and also to identify future studies needed to expand the

Pilot Project; (b) to recommend technical assistance programs and training

and education projects that would provide pertinent support to developing

countries to enable them to establish marine pollution monitoring activities.

These Proceedings contain summaries of, plenary speeches by invited guests,

summaries of papers given at the Symposium and the Report on the Workshop to

support the Pilot Project on Marine Pollution (Petroleum) Monitoring.

vii
MARINE POLLUTION MONITORING (Petroleum)

SYMPOSIUM AND WORKSHOP

Conference Coordinator, R. C. Junghans, NOAA

Program Committee

R. C. Junghans, NOAA, Chairman

S. P. Cram, NBS

J. F. Hebard, NOAA

R. B. Johnson, NBS,

S. R. Torrence, NBS

A. Georgilas, NOAA

K. Freed, NOAA

R. C. Junghans, NOAA, Chairman

W. B. Chappel, MarAd

P. E. Lehr, NOAA

G. C. Steinman, MarAd

A. Tolkachev, lOC/UNESCC

. Hughes, NOAA

. Chappel, MarAd

. Martin, NBS

. Stang, NBS

R. S. Maddock, NBS

R. A. Zachariason, NOAA

Arrangement Committee

Chairman K. H

W. B

R. F

K. C

Publications Committee

*******

Invited Speakers

R. W. Roberts

R. M. White

A. I. Simonov

B. E. Willard

P. Thacher

A. Tolkachev

E. B. Wilson

S. Hori

S. R. Galler

H. F. Casey

R. M. Morse

M. E. Stansby

J. J. Nachtsheim

T. A. Wastler

S. A. Wallace

T. S. Austin

I. T. Thompson

II. E. M. Levy

M. Ehrhardt

III. R. R. Hiltabrand

J. R. McNesby

Topical Session Chairman

IV

V,

VI,

J. W. Earring ton

F. T. Weiss

M. Gruenfeld

M. E. Stansby

Final Plenary R. L. Lehman

B. J. Thompson

A. Zsolnay

R. H. Pierce, Jr.

Rapporteurs

R. C. Clark, Jr,

T . Joyner

viii
CONTENTS

Invited Papers Page

WELCOMING ADDRESS 1

Richard W. Roberts

UNITED NATIONS ENVIRONMENT PROGRAM EARTHWATCH

AND MARINE POLLUTION 3

Robert M. White

SCIENTIFIC PROBLEMS OF THE SYSTEMS FOR GLOBAL MONITORING

AND INVESTIGATION OF OIL POLLUTION IN THE WORLD OCEAN .... 9

A. I. Simonov

ENVIRONMENTAL QUALITY 15

Beatrice E. Willard

COMMENTS 19

Peter Thatcher

PILOT PROJECT ON MARINE POLLUTION MONITORING

UNDER THE FRAMEWORK OF IGOSS 21

A. Tolkachev

SURVEY ANALYSES FOR PETROLEUM DERIVED HYDROCARBONS

IN THE OCEAN 27

Sadakiyo Hori

ANALYSIS STANDARDS AND INTERCOMPARISON OF DATA 29

Sidney R. Caller

MARITIME CONSIDERATION OF OIL TRANSPORTATION . 33

Howard F. Casey
Invited Papers (continued) Page

MARINE POLLUTION DATA ARCHIVING AND EXCHANGE 41

Richard M. Morse

BIOLOGICAL ENVIRONMENTAL EFFECTS 45

Maurice E. Stansby

MARITIME CONSIDERATIONS 49

John J. Nachtsheim

REGULATORY FUNCTIONS 57

T. A. Wastler

REGULATORY FUNCTIONS AS RELATED TO VESSEL CONSTRUCTION

AND OPERATION 61

S. A. Wallace

CONCLUDING REMARKS 67

Thomas S. Austin

Contributed Papers

Topical Session I. Sampling Methods and Techniques: Oil Slicks,

Tar Balls, and Particulates

QUANTITATIVE MONITORING AND VARIABILITY OF PELAGIC TAR

IN THE NORTH ATLANTIC 75

James N. Butler and Byron F. Morris

TAR BALL LOADINGS ON GOLDEN BEACH, FLORIDA 79

W. A. Saner

X
Contributed Papers (continued) Page

TAR BALL SAMPLING IN THE WESTERN NORTH ATLANTIC 83

William E. McGowan, William A. Saner and Gary L. Hufford

EVALUATION OF THIN FILM OIL SAMPLERS 85

W. J. Chang, J. R. Jadamec

OIL SPILLAGE MONITORING, SAMPLING AND RECOVERY SYSTEMS .... 89

J. G. Zahka

SAMPLING OF OIL SPILLS AND FINGERPRINTING

BY INFRARED SPECTROSCOPY 91

Chris W. Brown, Mark Ahmadjian and Patricia Lynch

A NEW INFRARED INSTRUMENT FOR MONITORING OIL FILMS

ON WATER 93

D. E. Wright and J. A. Wright

MAPPING AND IDENTIFICATION OF OIL ON WATER BY THE USE

OF AN AIRBORNE LASER SYSTEM 95

G. K. Schwemmer and H. H. Kim

MOVEMENT OF SPILLED OIL IN SAN FRANCISCO BAY AS PREDICTED

BY ESTUARINE NONTIDAL DRIFT 97

T. J. Conomos

OIL POLLUTION ALONG THE INDIAN COASTLINE 101

S. N. Dwivedi and A. H. Parulekar

Topical Session II. Oil in Water: Sampling and Analytical Methods

SAMPLING ERRORS IN THE QUANTITATION OF PETROLEUM

IN BOSTON HARBOR WATER 109

A. M. Ahmed, M. D. Beasley, A. C. Efromson and R. A. Kites

xi

1
Contributed Papers (continued) Page

HYDROCARBON CONCENTRATIONS IN SEAWATER ALONG THE

HALIFAX-BERMUDA SECTION: LESSONS LEARNED REGARDING

SAMPLING AND SOME RESULTS 113

Donald C. Gordon, Jr. and Paul D. Keizer

DETERMINATION OF AROMATIC HYDROCARBONS IN SEA WATER USING

AN ELECTROLYTIC STRIPPING CELL 117

S. P. Wasik and R. N. Boyd

DETERMINATION OF AROMATIC AND TOTAL HYDROCARBON CONTENT IN

SUBMICROGRAM AND MICROGRAM QUANTITIES IN AQUEOUS SYSTEMS

BY MEANS OF HIGH PERFORMANCE LIQUID CHROMATOGRAPHY 119

A. Zsolnay

DETERMINATION OF C^-C^^ HYDROCARBONS IN WATER 121

Clayton D. McAuliffe

SUSPENSIONS OF CRUDE OILS IN SEA WATER: RAPID METHODS

OF CHARACTERIZING LIGHT HYDROCARBON SOLUTES 127

Roger M. Bean

MEASUREMENT AND CHARACTERIZATION OF NONVOLATILE HYDROCARBONS

IN OCEAN WATER 131

R. A. Brown, J. J. Elliott and T. D. Searl

IDENTIFICATION, ESTIMATION AND MONITORING OF PETROLEUM

IN MARINE WATERS BY LUMINESCENCE METHODS 135

A. W. Hornig

RECENT DEVELOPMENTS IN THE IDENTIFICATION OF ASPHALTS

AND OTHER PETROLEUM PRODUCTS 145

F. K. Kawahara

xii
Contributed Papers (continued) Page

IDENTIFICATION OF HYDROCARBONS IN AN EXTRACT FROM ESTUARINE

WATER ACCOMMODATED NO. 2 FUEL OIL 149

R. H. Bieri, Ann L. Walker, B. W. Lewis,

G. Losser and R. J. Huggett

Topical Session III. Standards and Intercomparison Criteria

THE ROLE OF STANDARD REFERENCE MATERIALS

IN ENVIRONMENTAL MONITORING 157

H. Thomas Yolken

STANDARD AND INTERCOMPARISON CRITERIA: TAR BALLS

AND PARTICULATE MATTER 161

Richard W. Traxler and Richard H. Pierce, Jr.

ANALYSES OF HYDROCARBONS IN MARINE ORGANISMS: RESULTS

OF IDOE INTERCALIBRATION EXERCISES 163

J. W. Farrington, J. M. Teal, J. G. Quinn, P. L. Parker,

J. K. Winters, T. L. Wade and K. Burns

IDOE-5 INTERCALIBRATION SAMPLE: RESULTS OF ANALYSIS

AFTER SIXTEEN MONTHS STORAGE 167

G. C. Medeiros and J. W. Farrington

USE OF LOW MOLECULAR-WEIGHT-HYDROCARBON CONCENTRATIONS

AS INDICATORS OF MARINE POLLUTION 171

William M. Sackett and James M. Brooks

FLUORESCENCE MONITORING STUDY AT OCEAN WEATHER STATION "P" . . 175

W. J. Cretney and C. S. Wong

xiii
Contributed Papers (continued) Page

Topical Session IV. Oil in Marine Organisms and Sediments:

Sampling and Analytical Methods

SAMPLING MARINE ORGANISMS AND SEDIMENTS FOR HIGH PRECISION

GAS CHROMATOGRAPHIC ANALYSIS OF AROMATIC HYDROCARBONS .... 181

Herbert E. Bruce and Stuart P. Cram

FIELD SAMPLING METHODS AND TECHNIQUES FOR MARINE ORGANISMS

AND SEDIMENTS 183

Dale Straughan

METHODS FOR ESTABLISHING LEVELS OF PETROLEUM CONTAMINATION

IN ORGANISMS AND SEDIMENT AS RELATED TO MARINE

POLLUTION MONITORING 189

R. C. Clark, Jr.

QUANTITATIVE DETERMINATION OF HYDROCARBONS

IN MARINE ORGANISMS 195

J . S . Warner

METHODS FOR TRACE ORGANIC ANALYSIS IN SEDIMENTS

AND MARINE ORGANISMS . 197

H. S. Hertz, S. N. Chesler, W. E. May, B. H. Gump,

D. P. Enagonio and S. P. Cram

LONG TEEM WEATHERING CHARACTERISTICS OF IRANIAN CRUDE OIL:

THE WRECK OF THE "NORTHERN GULF" 201

D. W. Mayo, D. J. Donovan, L. Jiang,

Robert L. Dow and John W. Hurst, Jr.

ANALYTICAL TECHNIQUES FOR ISOLATING AND QUANTIFYING

PETROLEUM PARAFFIN HYDROCARBONS IN MARINE ORGANISMS 209

R. C. Clark, Jr., and J. S. Finley

xiv
Contributed Papers (continued) Page

DETEEMINATION OF HYDROCARBONS IN MARINE ORGANISMS

AND SEDIMENTS BY THIN LAYER CHROMATOGRAPHY 213

L. Hunter, H. E. Guard and L. H. DiSalvo

DETERMINATION OF EXTRACTABLE ORGANIC MATERIAL AND ANALYSIS

OF HYDROCARBON TYPES IN LAKE AND COASTAL SEDIMENTS 217

J. W. Blaylock, R. M. Bean and R. E. Wildung

HYDROCARBONS IN BLUE MUSSELS FROM THE KIEL BIGHT 221

Manfred Ehrhardt and Jurgen Heinemann

Topical Session V. Tar Balls and Particulate Matter:

Analytical Methods

IDENTIFICATION OF MINERAL OILS BY FIELD IONIZATION

MASS SPECTROMETRY 229

M. Anbar, M. E. Scolnick and A. C. Scott

PELAGIC TAR IN THE GULF OF MEXICO AND CARIBBEAN SEA 233

L. M. Jeffrey,- W. E. Pequegnat, E. A. Kennedy,

A. Vos and B. M. James

MARINE ENVIRONMENTAL MONITORING: TRACE ELEMENTS

IN PERSISTENT TAR BALL OIL RESIDUES 237

Milton H. Feldman and David E. Cawlfield

DISTRIBUTION OF TAR BALLS AND NEUSTON SAMPLING

IN THE GULF STREAM SYSTEM 243

K. Sherman, J. B. Colton, R. L. Dryfoos,

K. D. Knapp and B. S. Kinnear

ESTIMATION OF THE MODERN OIL POLLUTION OF THE

NORTH ATLANTIC WATERS 245

A. I. Simonov, S. G. Oradovski and A. A. Justchak

XV
Contributed Papers (continued) Page

Topical Session VI. Biological Assessment

VALUE OF OIL POLLUTION MONITORING IN MARINE ORGANISMS .... 249

Gilles La Roche

EFFECTS OF OILS ON BALTIC LITTORAL COMMUNITY, AS STUDIED

IN AN OUTDOOR MODEL TEST SYSTEM 251

M. Notini and A. Hagstrom

HYDROCARBON CONTENT AND CHLOROPHYLL CORRELATION IN THE

WATERS BETWEEN NOVA SCOTIA AND THE GULF STREAM 255

A. Zsolnay

EFFECT OF AN OIL SPILL ON BENTHIC ANIMALS

IN THE LOWER YORK RIVER, VIRGINIA 257

M. E. Bender, J. L. Hyland and T. K. Duncan

MARINE POLLUTION BY CARCINOGENIC HYDROCARBONS 261

James B. Sullivan

AUTHOR INDEX (Contributed Papers) 265

KEY WORD INDEX ^ 267

Report of the WORKSHOP ON MARINE POLLUTION MONITORING .... 271

LIST OF PARTICIPANTS IN WORKSHOP 301

SYMPOSIUM PARTICIPANTS, AUTHORS AND SPEAKERS . . . . . . .307

XVi
Welcoming Address

Dr. Richard W. Roberts

Director, National Bureau of Standards

Department of Commerce, USA

Many poets have looked to the sea for inspiration. They've seen it as

a mystery, as a barrier that separated people. They've pictured sea monsters

and various perils. But two centuries ago Samuel Coleridge painted a very

dramatic picture of a polluted ocean in the Rime of the Ancient Mariner . It strikes uncomfortably close to home these days. He said:

"The very deep did rot...

Yea, slimy things did crawl with legs

Upon the slimy sea. About, about, in reel and rout

The death-fires danced at night.

The water, like a witch's oils.

Burnt green, and blue and white.

Things aren't that bad. But the nations of the world have to view the sea as a common territory whose wealth we can share only so long as we pre- serve and protect it.

In March of 1968 the President of the United States endorsed the concept

of an International Decade of Ocean Exploration. He stated:

"The task of exploring the ocean's depth for its potential

wealth - food, minerals, resources - is as vast as the seas themselves. No one nation can undertake that task alone. As

we have learned from prior ventures in ocean exploration,

cooperation is the only answer."

Two months later the International Oceanographic Commission adopted a formal

recommendation supporting the Decade idea coordinated on a world-wide basis.

Further endorsements came from the United Nations General Assembly.

In the first year of the Decade's existence, three areas were chosen for

priority attention:

(1) Environmental quality,

(2) Environmental forecasting, and

(3) Seabed assessment.

The commitment to sharing the task of exploring and protecting the oceans brings us together this morning. Representatives from over 75 nations

are here to join with the sponsors of this conference - IOC, the World

Meteorological Organization, the National Oceanic and Atmospheric Administration,

the Maritime Administration and the National Bureau of Standards. We have a two-fold purpose:

1
First we want to develop working guidelines for an international pilot project to monitor marine pollution. And we want to focus on the problems and

advances in the measurement and characterization of petroleum hydrocarbons

in the marine environment.

On behalf of all of NBS, I want to welcome you to the Bureau. You are visiting one of the largest physical science laboratories in the world. Our

work in standards development spans a broad range of activities because,

after all, standards are the currency of science. This currency is based on accurate measurement. In the area of marine pollution, we're not yet at the

minting stage. Your job, beginning with this conference, is to find the best

ways of measuring and monitoring hydrocarbons. The focus is very specific,

and there's much to build on. But only by working together can the nations

of the world build toward a solution to a global problem.

2
United Nations Environment Program EARTHWATCH

and Marine Pollution

Dr. Robert M. White, Administrator

National Oceanic and Atmospheric Administration

Ladies and gentlemen, our government of the United States is very pleased

to have the opportunity to host this Symposium on Marine Pollution Monitoring

which is sponsored, as you know, by the Intergovernmental Oceanographic

Commission of UNESCO and by the World Meteorological Organization. On behalf

of our government I would like to express to all of our foreign colleagues

a hearty welcome. You are in Washington at the right time of year and I know you will enjoy your stay here.

There is no need to emphasize to this group that marine pollution is

clearly a threat both to the environmental and the economic values we all

consider so important, and we are certainly dealing with a problem that is

worldwide in scope and that affects both the developing and the developed

nations of the world.

Marine pollution, as we all know, in our estuaries, in our coastal

waters, and in the open ocean has myriad effects and, in many cases, effects

which are poorly known insofar as the entire marine ecosystem is concerned.

We are aware and concerned that there are significant reductions caused by

such marine pollution to the capacity of our ocean waters to sustain

economically important fisheries. We are aware that marine pollution reduces

the recreational attractiveness of coastal waters, and so has a very serious

adverse impact on economic values related to tourism. We are aware that

marine pollution affects human health through contaminated fish, and, over

the years, have seen many incidents in many countries of concern to all of

us. These impacts of marine pollution of course are one of the reasons we

are gathered here, and we are addressing a problem area that is intensifying

rather than diminishing. It is a problem which is intensifying because our populations are increasing and our oceans are being used increasingly as avenues for the transport of energy resources as the world seeks to provide

increased oil and gas resources by extraction from the seabed. And clearly

on the horizon, is ocean mining for hard minerals on the sea floor. The

problem is caused internationally and can only be solved internationally.

The ocean is fundamentally a fluid and what happens in one place in the oceans affects other places in the ocean. And so we have need for information

about the state of pollution in the oceans. We want to know many things.

We want to know the geographical extent of pollutants. We want to know about

their concentration and the manner in which the oceans disperse or concentrate

the pollutants. We want to know about the effects of pollutants on human

health. And we would like to be in a position to be able to forecast the

consequences of man's actions on the state of ocean pollution.

Now it is not that this problem hasn't received attention. It has

received attention by many bodies over the many years, the latest of which,

of course, has been that of the United Nations Environment Program. In

3
February, that program had an Intergovernmental Working Group meeting in

Nairobi on what is now called the Global Environmental Monitoring System, an element of the EARTHWATCH program which I will be discussing later in my

talk.

But the point I want to make here is that the importance of monitoring

ocean pollution was recognized during the course of that conference and such

monitoring was established as one of the seven major goals of the Global

Environmental Monitoring System. Hopefully, the Intergovernmental Oceanographic Commission and the World Meteorological Organization, through the

Integrated Global Ocean Station System (IGOSS), will be stimulated and

supported by the United Nations Environment Program and will be able to

translate this general concern into a working international effort.

I think it would be useful to ask where we now stand with respect to the

establishment of a marine pollution monitoring system. As I have indicated, we have had many studies and analyses which identify the scope of the problems

which face us, and tell us something about our present state of knowledge

and where our principal efforts should be devoted. In a very general sense,

I think we could say that the data we presently have on the state of ocean

pollution is fragmentary at best. I think we can also say that the techniques

and instrumentation for measuring pollutants of interest are principally

laboratory methods and for only a few do we have methods adequate for

systematic and routine data collection.

I think we must admit that we have yet to institute in any real way an international system for the monitoring of this ocean pollution. Hopefully,

the Marine Pollution Monitoring Pilot Project, for which this S3nnposium will

be a precursor, will be a first step in this direction. So this Symposium

is a key element in laying the foundations for such a monitoring system.

I doubt that there is anybody in this audience who has dealt with problems of monitoring marine pollution who thinks that the task is easy. Quite

the contrary. Even for very well stated problems, the costs that we face are large in that the time required for obtaining systematic results will be

extensive. I think we all realize this.

I am reminded of one example in which my own organization and the

National Bureau of Standards participated a few years ago. In the early 1960's,

great concern was expressed by many scientists in the United States about the

effects of insecticides and herbicides on photosynthesis and associated

oxygen production because of possible effects on phy toplankton. We mounted

a program to attempt to measure whether there indeed had been any worldwide

changes in the atmospheric oxygen content. It took four years of joint

effort by the National Oceanic and Atmospheric Administration and the

National Bureau of Standards to measure oxygen content around the world and

to demonstrate that, indeed, this effect about which people were concerned

was not really there. I point this out only to indicate that here is a case

of a very well-defined problem and that it was no easy task to implement even when you know what you wanted to do.

A
We need now to move into action, it seems to me, with a realistic plan

of international participation in a program, and the program should start

with the measurement of simple pollutants. To do this is currently within

our capability. The program also should provide for the necessary research

and development of the new techniques and instrumentation that will be

required to measure other parameters. I think there is no lack of general

agreement on what some of the things are that we must measure. Studies

such as those Included in the Studies of Critical Problems of the Environment;

studies by various organizations in my country, our Academy of Science, and

various government agencies; and studies by international groups such as the Special Committee on Problems of the Environment of the International

Council of Scientific Unions, sub-groups of the Intergovernmental Oceanographic Commission, and the recent Intergovernmental Working Group on the

Global Environmental Monitoring System. All these came to roughly similar

conclusions about the nature of pollutants that we ought to be measuring in

the oceans and the priorities for measuring them. These, of course, include

petroleum, chlorinated hydrocarbons, and various toxic metals.

In my country there is now deep concern and there currently is action

on problems dealing with the monitoring of marine pollution. There has

been action by our Congress in passing laws that provide the authority to

undertake such monitoring activities. Laws, such as our Marine Protection,

Research, and Sanctuaries Act of 1972, for example, provide for monitoring

and research on various aspects of ocean pollution. Amendments to our Water

Pollution Control Act of 1972 provide for various kinds of water quality

surveillance systems.

The President of the United States, in connection with our country's

drive to increase the rate of extraction of oil and gas from our Continental

Shelf, has directed extensive studies of a baseline nature be undertaken to

give us the necessary information. We have a number of different kinds of

monitoring programs now underway in the United States. There are baseline

studies such as the GEOSECS Program of the National Science Foundation. There

are studies, such as that being organized by my own organization, dealing with

pollution effects from ocean dumping in the waters off the east coast of the

United States.

I have mentioned activities now underway to establish baseline information over our Continental Shelf in connection with oil and gas developments. In the hall here, you probably saw the display of what we call our MARMAP Program, our Marine Resources Monitoring and Prediction Program, which

seeks to acquire information about the distribution, not only of fish stocks,

but on the various kinds of contaminants that might affect fish stocks. We

also have extensive programs to examine the various kinds of microconstituents

in all of the commercially important species of fish used in the United States.

There is extensive technology development underway in the United States some

of which you will hear about in the conference this week.

Internationally, there is similar concern and there has been action

even prior to the United Nations Conference on the Human Environment at

Stockholm. There were many conferences attempting to define what we ought

to do about ocean pollution, but at Stockholm, as part of the conference

5
which lead to the United Nations Environment Program, there was established

the program called "EARTHWATCH, " a program designed literally to place the

earth and various aspects of it under a watch—and I use this term advisably

and one part of this program is the Global Environmental Monitoring System

(GEMS)

.

The United Nations Conference at Stockholm has led to the establishment

of the United Nations Environment Program and the establishment of a voluntary

fund of $100 million for use over a period of five years. This fund now

can be used for a variety of purposes dealing with environmental problems of concern to the nations of the World.

Now the EARTHWATCH Program involves many things besides monitoring. It

involves problems of evaluation, research and information exchange. But the

most immediate problem is that dealing with the monitoring of the global

environment. The United Nations Environment Program Governing Council

meeting in June of 1973 called for the early development and implementation

of the Global Monitoring and Information Referral Systems of the EARTHWATCH

Program which in turn led to the recent February (1974) meeting in Nairobi

of the Intergovernmental Meeting on Monitoring. At that meeting, a number

of principles were approved that would govern the inplementation of this

Global Environmental Monitoring System. For example, one of the principles

is that it make maximum use of existing national and international systems.

This points to the importance of developing the Integrated Global Ocean

Station System as one of the existing international systems. The meeting

emphasized the need to move ahead —now—^with the monitoring of critical

environmental conditions for which we have the scientific and technological

capability. It recognized the need to assist developing nations to enable

them to participate in this worldwide activity of concern to all. I indicated

earlier that one of the seven goals of this Global Environmental Monitoring

System, now internationally agreed upon, was indeed the study of man's impact

on the ocean. Among the other goals, of course, were questions of human

health, natural disasters, food contamination, man's impact on the climate,

and the stability of ecosystems. The major point here is that we now have

worldwide agreement within the United Nations Environment Program to move

ahead with one of its major goals, a program to study man's impact upon the ocean—and that means ocean pollution.

At this meeting there was also agreement on a priority list of pollutants

to be studied. While there were some surprises in the priority ordering of

this list of pollutants, I don't think the list will take any of you by

surprise. It merely emphasizes that petroleum and petroleum products remain

among the critical elements that we need to monitor in the oceans.

It is my hope that as a result of these decisions taken within the United

Nations Environment Program and as a result of the fact that there is now a funding mechanism through the voluntary fund of the United Nations Environment

Program, that it will be possible to move ahead with this Integrated Global

Ocean Station System (IGOSS) which is sponsored by the Intergovernmental

Oceanographic Commission and the World Meteorological Organization. Already,

we can begin to see some of the results of some of the funding of that program. The United Nations Environment Program has already provided support

6
for the GESAMP (Group of Experts on Scientific Aspects of Marine Pollution)

.

They have provided support for the travel of a number of the delegates to

this Symposium, and they have provided support for certain intercalibration

efforts between the Intergovernmental Oceanographic Commission and the

International Atomic Energy Agency. And, if we can come up with appropriate

plans to demonstrate what it is that we can and want to do in the way of

international monitoring of ocean pollution, I hope that we can convince them

that this would be an area for worthy expenditure of the funds of the United

Nations Environment Program.

So I think the timing is right for this Symposium. There are resources

available to move ahead with a program, and there are plans for the Pilot

Project. I think we have the right vehicle to do the job in this joint

program of the IOC and WMO, and I know that with Symposia such as this and

the results that will emanate from them, we can move ahead.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

7

* Scientific Problems of the Systems for Global Monitoring and

Investigation of Oil Pollution in the World Ocean

Professor A. I. Simonov

Oceanographic Institute

U.S.S.R.

Mr. Chairman, ladies, and gentlemen. First, let me thank you for the

opportunity to address this esteemed gathering on a very important and serious

subject. Please accept my apologies for using more than my allotted time;

this is necessary because simultaneously translation of my report, as I read it in Russian, is a slow process.

Mr. Chairman. At first I planned only to comment on the text of a draft

program of global observations and explorations presented by me last year to

the Intergovernmental Oceanographic Commission, (First Session of the International Coordination Group for Global Investigations of Pollution in the

Marine Environment) . This numbered report was distributed to Members of the

Commission in both English and Russian language versions. Later, I decided

that because two years had passed since the program was initiated, a more

complete discussion was warranted.

In my report I will describe or comment on the following items. First,

the background of the problem; second, the global character of the problem

under consideration by this gathering; third, the role of hydrodynamic factors

in the movement, dispersion, and accumulation of harmful pollutants; fourth,

the kinetics of dispersion and disintegration of the various forms of oil

and oil products in the marine environment and the disintegration forms of

these oils; and, fifth and last, I will discuss the main elements of the

scientific basis for a global system for monitoring and investigating oil

pollution in the world's oceans. Thus I have divided my report into five

sections.

In considering the background of the problem, we must first consider the

nature of the problem. As I see it, the nature of the scientific aspects of

protecting the marine environment from pollution can best be determined by

working out scientifically based recommendations for regulating or completely

prohibiting the discharge of wastes containing petroleum hydrocarbons.

Accordingly, processes utilizing harmful substances should constantly be

monitored so that waste disposal methods can be developed leading to the

complete elimination of pollution effects in the water medium and on ecological

systems. This recommendation covers a wide range of problems. Among the most

important actions needed to deal with the problem are the following:

* This is an English translation made from the speech given in Russian and

recorded on tape. Due to technical difficulties beyond our control, clearance

by the author has not been obtained.

9
(1) A continuous and systematic monitoring and evaluation of oil and

oil product pollution conditions in the waters of the world oceans.

(2) Studies of the increasing utilization of oil and oil products as these uses affect the seas.

(3) The development of regulations concerning the discharge of

substances containing petroleum originated hydrocarbons into the

sea

.

The difficulties of dealing with these problems lies in their complexity

and their interdisciplinary nature. The level of current knowledge in the

various oceanographic disciplines, such as the chemistry and the kinetics of

the seas, requires a considerable amount of development to enable their use

in the solution of these problems. And the last, but not the least of the

factors that must be considered, is the ubiquitous nature of the world's

oceans. The seas, like the atmosphere, know no national boundaries; pollution

originated by one nation is not the problem of just that nation but of all

the nations of the world. The international convention that met in London

in 19 72 agreed that oil and oil products should be considered the most

widespread pollution substances affecting the world's oceans. Various sources estimate that ten to fifteen million tons of oil substances are dumped into

the oceans annually. No doubt this pollution will increase at an ever growing

rate as oil production increases and as the major part of the production is

moved from land to the continental shelf and farther out to sea. I would like

to remind you of the catastrophic effects of oil and oil products on the

biotic regime of the oceans. Oil has extremely harmful effects on a number

of links in the biological chain, links that were created over mtold millenia.

Together with this, oil films on the oceans have a considerable effect on the

exchange of heat, gases, and water vapor between the sea and the atmosphere.

It is not too far fetched to predict that extensive and persistent oil films

on the surface of the seas could have serious effects on the climate of the

earth and the oxygen content of the atmosphere.

Now to my second point; the global character of the oil pollution problem and the proof that the problem is truly global. Until recently, we had no data with which to characterize the degree or extent of pollution of the

waters of the world by oil and oil products. Many of you here will remember

an address by Tor Hyerdahl at the London conference during our preparations

for the Stockholm conference. Hyerdahl reported on his visual observations

and impressions on the extent of oil pollution in the North Atlantic. At

that time, his was perhaps the only direct source of information on such

pollution. This report inspired experts from a number of countries, including the USSR, to make a series of observations of pollution conditions in the

North Atlantic and the seas that wash the coastal areas of the European

continent during the period 1971-73. The primary reason for these observations

was that, at that time, both the semi-enclosed Baltic Sea and the completely

open Barents Sea were heavily polluted by oil and oil products. A number of

very important conclusions about the character of oil pollution in certain

parts of the oceans were made possible by analyses of these observations.

The most important conclusion drawn was that oil pollution in the oceans is now global. Today, it is equally probable that petroleum hydrocarbon pollution

exists and can be observed in any part of the world's oceans, including the

10
continental seas, the coastal waters, and even in the open oceans. Another

important conclusion is that fields of oil pollution, which originate

primarily near the shores, spread out to cover entire inland seas and even certain large areas of the open oceans. The seas that wash the edge of the

European continent are polluted with oil and oil products; the amounts of

pollution exceed the Soviet Union's maximum allowable concentration of 500

parts per million. The Baltic, the North Sea, the Irish Sea, the Bay of

Biscay, and the Tyrrhenian and Ionic Seas are entirly covered by oil pollution.

While the concentration of pollutants in these relatively enclosed seas decreases with distance from the shore, the concentrations at distances

hundreds of kilometers from shore are still greater than the USSR allowable

maximum. The same conditions obtain in other parts of the open oceans. The

highest concentrations of pollution substances have been measured in nearshore areas and in the vast, relatively quiet areas of the open ocean to

which they are carried by the Gulf Stream and the North Atlantic current. (I

will deal with this problem in detail in my paper tomorrow.) Thus, at present,

we have a basis to believe that oil pollution is quite global in character.

I would like to note that these conclusions contradict to some extent those

stated by Menaham and others in their report entitled "The Content of Stable

Hydrocarbons in the Sea Along the Line of Tanker Ships." Their conclusion is

that oil basically spreads in a thin layer up to ten meters in depth. It seems to us that this conclusion is not completely substantiated because the

water samples were taken only in the layer from the surface to a depth of

ten meters. Further on, I will show that oil pollution can be found deeper —

much deeper — and that its spread depends on the vertical circulation, the

position of the thermocline, the form of the oil products, and the time they

have been in the water.

And now the third section of my report. Here I will discuss the

influence of hydrodynamic factors on the spreading, dispersion, and accumulation of oil pollutnats. Analyses of the horizontal spread of petroleum

pollutants shows that minimum concentrations occur in the fast moving water

in the middle of ocean currents and maximum concentrations in the peripheral

regions of turbulence. The vertical distribution of oil products is multilayered in the extreme. The greatest numbers of layers containing concentrations of oil were found between the surface and ten meters down and again

between fifty and one hundred meters down. Sometimes these concentrations

were registered at even greater depths. The nonuniformity of the spreading

of oil products is attributable to their variation in form, the length of

time they have been in the water, and the peculiarities of the circulation

and vertical structure of the water. In sea waters, oil products can take

many forms: emulsions, floating films, lumps, and even solutions in small

amounts. Thus, oil products, which are basically in the form of dispersed

particles that increase in weight with time, will, under normal conditions,

be carried from dynamically active zones under the influence of the Coriolis

acceleration and transverse currents to relatively calm zones where they will

accumulate gradually. Bearing this in mind, we can expect that accumulations

of oil pollutants will gather both on the surface and to some depth on the

outer periphery of cyclonic ^irls and in the inner zone of anticyclonic

whirls. This is completely confirmed by measurements taken in the North

Atlantic (which I will report on in my paper tomorrow)

.

11
The fourth section of my report deals with several of the most important

chemical and physical aspects of the nature of pollution in the sea. I will

be brief because these problems will be dealt with in detail later in our

Symposium. Experimental investigations on how the concentration of oil

changes with time show that the first reaction that takes place is saturation

of the sea water by oil. This process can last for as long as ten days.

After saturation has occurred and a state of equilibrium has been reached,

the interaction between microchlorine and oil initiates a process of intensive

disintegration of oil products, which can last for ten, fifteen, or as long

as twenty days. After that, the speed of disintegration slows up considerably.

This experiment reveals the characteristics and the general features of the

disintegration of oil products under the influence of chemical and microbiological factors. Experiments on natural models have shown that physical

and chemical oxidation play very important roles in the disintegration of oil

products; this is a type of free-radical process. About sixty percent of the

oil is decomposed by chemical and physical processes which act in a fashion

similar to the process that causes monomolecular reactions. Together with

these experiments, we initiated steps to investigate differentially the

processes involved in the disintegration of oil components. The results of

these investigations show that, first, normal algae disintegrate very rapidly

and then the aromatic hydrocarbons begin to disintegrate. This process takes

place at a slower rate because disintegration of the aromatic hydrocarbons

requires larger amounts of oxygen. Our results are confirmed by the con- clusions reached by a number of American experts who have shown that all

petroleum hydrocarbons can be oxidized by bacteria. Hydrocarbons with long

chain structures can be destroyed faster than those with short chain

structures. Many aromatic hydrocarbons are less subject to oxidation than are petroleum hydrocarbons with direct or branched chains. It is our impression that the aromatization of molecules makes their micro-oxidation

difficult, perhaps because of their inherent stability. For a number of

the aromatic hydrocarbons investigated, a characteristic feature is that

oxidation takes place because of the presence of short-chain proteins. In

parallel with this investigation, we investigated the role of micro-organisms

in the oxidation of oil products. It has been stated that the period of

quickest reaction in the disintegration process is speeded up by the initiation

of oil oxidation processes and by the actions of all of the heterotropic

micro-organisms. In recent papers, the problems of the chemical nature and

the physical and chemical characteristics of the oil oxidizing process are considered according to the hydroperoxide theory of branched chain oxidation,

the details of which were worked out for hydrocarbons in the liquid phase

by Emmanual ( ? ) . It was stated that hydroperoxide, which is the initial

product of oxidation, is responsible for the degenerative branching out of

complex chain oxidation. On the basis of this information, scientists of

the Soviet Union have elaborated methods for controlling free-radical processes in the physical and chemical utilization of products such as petroleum

hydrocarbons. In concluding this section of ay report, I would like to

mention that the period of semi-disintegration of oil under similar conditions

may be as long as fifty to seventy days, and that the later period — when

the disintegration is slow — is prolonged and of indefinite duration. So

the experts, including scientists from the countries sponsoring this Symposium,

12
are absolutely correct in asserting that petroleum-originated hydrocarbons

decompose in the same way that other natural hydrocarbons have decomposed

during geological epochs in the past. Because of these principles, concentrations of oil can and do occur in the oceans and in the sediment, particularly under low temperature conditions.

And now for the fifth and final section of my report in which I will

speak of the main scientific principles for a global system of investigating

and monitoring oil pollution in the world ocean. I would like to remind you

that the observations mentioned above make it possible to define the characteristics of this system. The principles we are concerned with are the

following: first, the system of observations should take into account the

latitude and the zonal changes in thermal conditions so we can study the

influence of different temperatures on oil degradation. Thus, this system

should extend from the Equatorial zone to the Arctic zone of the North

Atlantic. Second , the observational system should be designed to take into

account the varied hydrodynamic conditions of the ocean. Some stations of the

network should be positioned in the main circulation currents so, on the

basis of observed motions, we can make quantitative predictions on the

transport of oil and oil product pollutants. Other observation points in

the s)^stem should be located in relatively calm zones of the ocean so we can

keep a continuous record of the accumulation of petroleum pollutants. For

example, in the North Atlantic, part of the network should cover the Gulf

Stream and the North Atlantic Current, as well as other parts of the system,

the northeastern sector of the Sargasso Sea and the Barents Sea. The third

consideration is toward monitoring the basic sources of oil based pollution.

These sources are the shorelines, the continental shelf, and the navigable

shipping routes along and connecting the continents. One does not have to

prove that the North Atlantic is the most polluted ocean region of the world;

the existence of large numbers of pollution sources in the area tells us intuitively that this is so. The principles just mentioned lead us to the

formulation of the fourth principle, which is that the system of observation

must be usable for solving the balance equation for oil pollution in this or

any other area of the world ocean. The balance equation mentioned is the one

I wrote for the IOC program, the Global Investigation of Pollution in the

Marine Environment (GIPME) . For the left part of the equation, I calculated

the increase of the concentration during a certain period of time, (e.g. , a year) , and for the right part of the equation all of the remaining components

of input and consumption of oil products in sea water. The solution for the

balance, in turn, requires that the observation system be so located that it

will account for the advection of oil, its redistribution in the vertical,

its sedimentation into soils, and its evaporation from the sea surface. The

observation system should provide not only for the taking of samples from the

surface and from below the surface, but also for measuring the specific

horizontal and vertical dimensions of sea surface oil films — bearing in

mind that the presence of these films can influence considerably the important

interactions between the atmosphere and the ocean. This requires observation

not only by surface vessels but also the location and observation of these

films by orbiting satellites.

13
These four principles require the organization of a complex system to

obtain meteorological, hydro chemical , hydrological, and hydrobiological

observations of the seas, the marine population, the bottom sediments, and

the air-sea boundary layer. These systematic observations should be carried

out in "benchmark" or "signature" regions. Regions not subjected to pollution

and for which standard smaples should be obtained, I call number one regions.

The number one benchmark regions should be investigated during the process

of reconnaissance over all oceans and at different geographical latitudes.

Simultaneously, systematic observations of number two, or polluted benchmark

regions, should also be carried out. Number two benchmark regions include

the most polluted areas of the world ocean, those areas near the months of

large rivers, large industrial and residential areas, areas of underwater

mining of minerals, petroleum, sand and gravel, and other areas of possible

sources of induced pollution. These special observations should be made periodically, say two to four times a year, using both region one and region two

benchmark stations as anchor points in the observational network. Before

activating a global observation system, it also will be necessary to determine

by reconnaissance the degree and specific distribution of oil pollution in

the open waters of the world ocean. These benchmark observations must be

available for planning the systematic observation and monitoring of oil

pollution. It apparently will be necessary to start with an experimental

demonstration project before setting up a global system. In my opinion, the

Atlantic Ocean would be the most suitable demonstration area. For any

observation network, it is necessary that we unify and standardize the

methods of chemical analysis, the measurement of physical characteristics,

and the means and methods of selection and storage of samples. These are

problems for consideration at this Sjrmposium.

This, in brief, is my report. I am sure that our Symposium will result

in a definite plan for an experimental demonstration project for observing

and monitoring oil pollution in the world ocean. Thank you for your

attention.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg , Maryland, May 13-17, 1974

(Issued December 1974)

.

14
Environmental Quality

Dr. Beatrice E. Willard

The President's Council on Environmental Quality

Thank you very much Mr. Junghans . It is a particular privilege for me

to address such an illustrious group on a very, very important topic to all

of us. This topic, as we are all aware, relates both directly and indirectly

to human survival on Planet Earth. During the past year, we at the Council

on Environmental Quality have focussed sharply on this topic. Just over a year ago, the President asked us to prepare for him a report on the environmental effects of oil and gas development on the Outer Continental Shelf of

the Atlantic Coast and the Gulf of Alaska, two areas that have never had any

oil and gas development. That report, delivered to the President on the 18th

of April, 1974, gave us an opportunity to summarize what is now known about

the environmental aspects of those areas and about the technological and

methodological aspects of controlling the acute and the chronic effects of

marine pollution from the variety of activities associated with off-shore

oil and gas development, not just from transporting oil.

It was sobering to all of us to see how little really was known about

the direct biological effects of oil and gas pollution in the marine environment. It was even more sobering to me, as a professional ecologist, to

realize that we were still not truly recognizing the real nature of the en- vironmental problems in this particular area. That is a rather strong

allegation and I would like to explain what I mean.

In the time that I have been serving on CEQ, I have noticed that policymakers often have a human tendency—^which all of us have, but which scientists

try to overcome, to conclude that because there are no dramatic, clear-cut,

immediate effects visible from oil spills, beyond a few birds drowned and a few feet of shoreline covered with oil for a few years, that there likely

are none. This conclusion is not surprising because it represents generally

the way in which people think; it is an example of the results of how without

scientific expertise, people go about gaining knowledge.

We have had a sophisticated scientific potential for obtaining ecological

and physiological knowledge for over a century. Some potential we have had

for two or three or four centuries, because man is very curious. He has been

finding out what species are there and what their habits are for centuries.

But, because the marine environment presents him with more of a challenge

than the terrestrial environment, man has not been able to find out as much

as is needed to understand the life requirements of marine animals, and

what the introduction of oil and gas into their environment means to them.

We now have the scientific techniques, considerable knowledge and the

potential to test the effects of oil and gas on all marine organisms. Some

will present more of a challenge than others. We have the ability to monitor

even subtle changes in both shoreline and pelagic marine ecosystems. Then

why is little being done compared to what needs to be done? It is because

"it is too expensive." Too expensive in whose terms? In the biologists'

15
terms? In the ecologists' terms? In Wall Street terms? In Government terms?

In petroleum companies' terms? And are we, when we are working out the expense, determining, in addition to the dollar value, all it will cost to find

out this information? And what it will cost us, if we do not find it out in

time to protect those populations on which we depend for food? Are we really

looking at costs from the human survival terms, as well as biological terms,

where time and evolutionary response play a big role in the equation?

I think all of you will agree that we are only beginning to understand

the vast ecosystems of the ocean. We must be sure that we are not selling

their needs short by a superficial short-range view of effects that we often

cannot determine fully within the short range of our rather inadequate attempts

to really understand the systems and the effects of oil on the systems.

Because we are at this point in time, because you are a very diverse

group, and because the demands of scientific discipline force us constantly

to become more and more specific, I want, this morning, to be more general.

This will enable us to focus on what I find a most helpful group of guidepoats

for better policymaking, ecological research, and environmental control.

This is a group of seven choices. All of us here will realize that the

choice intelligently can only be made in one direction. This is a choice

between doing what is most economically expedient at the moment and recognizing, utilizing, and living by a group of scientific principles of ecosystem

operation. I think all of you would agree that we have to choose obeying

principles of ecosystems, even though it may take a certain amount of rear- rangement of our own viewpoint, rearrangement of what we are willing to accept

as true, as a result of what we believe our own five senses are telling us.

To me, the most important priaclple is that everything affects everything

else, either directly or indirectly. This is a valuable guiding principle,

not only for ecology, but for all activities of humankind. The environment,

ecosystems, social systems, etc. are wholistic, integrally connected, and

interdependent

.

This one principle leads me to a very conservative viewpoint on how we

should treat the oceans of the world. But it is not easy for non-biological,

non-scientific people to accept, because they have a very difficult time

believing that the actions that they take today will have ramifications a hundred years, a thousand years, and even ten thousand years from now, because

they cannot see that far into the future. Unfortunately, we do not have the

scientific background to give them that vision. You and I have to provide

that for them. I want to compliment Dr. White for having this Sjanposium,

where we can get together to really plan how to research the knowledge for

them to use.

The second guiding principle of ecosystems is a self-evident choice to

those of us who are familiar with the natural world. Yet it comes as a revelation to those not trained in the scientific disciplines. This principle

is that the whole biosphere of Earth is divided into systems. We, as ecologists

call them ecosystems. In them, all living things have specific roles to play.

This is difficult for us to accept when we believe that some of those roles are not useful to man. Some of the roles are even detrimental to man. We

16
could all do without mosquitos if we had our emotional choice. A friend of

mine points out that if he had been given the job fifty years ago to do away

with the fifty most obnoxious plants, he undoubtedly would have done away with

that awful bread mold, penicillin. That action would have deprived man of

a valuable medicine. I think that intellectually all of us realize that all

of the natural phenomena eventually are going to be shown to be directly and

indirectly very important to us. But this fact is sometimes hard to sell

today.

The third principle is that all materials cycle, but energy does not.

This principle is one which we have had to come to grips with in the last

eight months, one which has made us realize we have to find new conservative ways

of using energy and new ways of finding out where the toxic substances which

we put into the system go. We are not anywhere close to this understanding,

as you know better than I.

Another principle that is hard to convince man of is that all living

systems and non-living systems have limiting factors. Engineers are quite

ready to accept that we can put only a certain amount of weight on top of a building before something happens; that if we exceed that weight, we would

ultimately have disastrous results. But they do not quite see that a natural

system also has these constraints. They feel, "We can handle that technologically,

we're always going to discover a technological fix for the problem." This may

be true, but if they were going to handle problems technologically for a building, they would design for possible limits before they tried to put the

weight on the roof; they would not design after the fact. I think that all we expect in ecosystem management is that we not put stresses on these systems

beyond what we know they are capable of absorbing. Yet all the time we push

in all directions —"cut more trees," "harvest more fish," "put more oil into

the water"—because we haven't seen the effects yet. But we have not lived

long enough for a lot of those effects to occur.

The fifth principle—closely related: all systems have a carrying capacity. This principle interacts closely with the fourth, but these concepts do

not come naturally to the non-biological, non-technical, non-scientific thinker.

He thinks automatically that "There is going to be a technological fix. Be- cause there will be a technological fix, the carrying capacity of any human

system cannot be determined. Therefore, there is no point in trying." This

is just like walking off the cliff without a belay rope.

The sixth principle is equally important, i.e., all ecosystems have a series of developmental phases through which they pass in their life histories.

These phases range from the simple, very unstable ones to the complex, stable

phases. We tend to believe that only the simple phases are productive for us.

The seventh and last principle is that as specialization occurs, more

diveristy comes into the system. With more diversity, they have greater and

greater stability. Constantly man is selecting against diversity. He thinks

he doesn't need California condors, and that grizzly bears aren't all that

important—without the knowledge of how these animals affect the total system.

It is as though we were electing not to recognize the value of molybdenum in

stress steel, when in fact the molybdenum, is the very thing that makes the

steel able to stand the stress.

17
As we candidly approach the marine systems—as you will in the next two

and a half days—seeking to understand their functioning and the needs for

that functioning, I am sure you will be able to determine more about basic

ecological costs and benefits, as well as the economic costs and benefits of

these systems to man. I am very impressed with a piece of work a famous

ecologist recently has done in Georgia. Dr. Eugene Odum of the University of

Georgia has found that saltgrass marsh along the Georgia coast, if filled so that it can support a shopping center or housing or an industry, would sell

at between $1,000 and $3,000 an acre. This value would happen once, because

it would likely be a terminal sale of land. But he has calculated that each

year the various jobs that those saltgrass marshes are doing for us: as nursery beds for many of our different fishes, as the source of nutrient for

the pelagic forms further out at sea, as cleaners of air and water pollution,

as buffers for the hurricanes, and many other contributions that he has

unearthed about this particular system, are worth an annual $85,000 per acre.

I am challenging you people in this room to see if you can arrive at

similar calculations to help us to convince people of the subtle but real

values of maintaining healthy ecosystems on Earth. When we have honestly

done this, choosing to recognize, accept, and use the basic principles of

ecology as governing—which they are—and not the man-made objectives that run counter to ecological principles, we will begin to experience greater

environmental quality on Earth. We will begin to do what the National Environmental Policy Act of out Nation demands of us, i.e., to "bring man into harmony

with his environment."

The ecologists would say it a little differently. They would say we

will begin to learn how to assist man in assuming his ecological niche on

Earth. I trust that we soon will accept this challenge, and solve the problems that lead to this objective. I look forward to what you can contribute

in this direction in the next few days.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

18
Dr. Peter Thatcher

Director, Geneva Liaison

Office of the U.N. Environment Program (UNEP)

Geneva, Switzerland

On behalf of UNEP's Executive Director, Maurice Strong, I would like to

express the hope that the results of your work here will contribute to the

goals governments have established for the UN Environment Program. We will

judge our ability to use the resources available to us to support the work

programs that are developed in groups such as this on the basis of the

obvious criterion, the degree to which they contribute to the objective of our programs.

What is the overall objective? Simply put, to preserve and enhance the

quality of the environment for present and future generations. It is clear

that knowledge alone is not sufficient to accomplish the objective. Unless

knowledge is presented in a form which is compelling to the decision-maker

at the national or international level, his decisions will continue to

reflect the fact that the data that comes out of the economic world, and the

immediate political world, is a good deal harder and more reliable than the

data that reaches him from the scientific world.

We have an opportunity to change this situation with regard to the

oceans, one which has been growing over the years, one which, if we fail to

exploit now in the next few years, may not arise again. The opportunity is

based on the political willingness that governments have registered to do

something about that part of this planet which lies outside the limits of

national sovereignty. At the Stockholm Conference we found a high level of

willingness by governments to commit themselves in general terms to the

actions that must be taken if man's effects on the oceans are to be reduced.

So I think that the burden comes right down on you to develop, with

precision, not only the parameters to be measured but the techniques involving intercalibration, particularly, on which rest the softness of so much of the data presently available to the decision maker. We must

acknowledge that we are using the oceans, we are using man's common concern

to protect the oceans, as one of the many devices by which to attack the

problem at the source. For example, most of the petroleum reaching the

oceans, still of course, comes from land. We have seen considerable progress

with regard to maritime sources. There are new laws and new conventions,

which have the capacity of binding states to adhere to new principles of

design with regard to vessels. There is the recent achievement in London of

an Ocean Dumping Convention, which attacks the broad problem of deliberate

waste, where nations have traditionally followed the natural geological

process of using the oceans as the garbage pail for waste they do not want

to dispose of on land. In recent weeks, the government of France has

achieved, I think, a very significant breakthrough in the form of an international agreement on the part of a number of European states to coordinate

their attack on marine pollutants which reach the oceans thru river input

and direct outflow. I think that the significance of this is that here is

19
a collective effort, for the first time, to go up the rivers, to go into

the municipal sewer system, to find out where the critical valves are that

must be turned off if any significant difference is to be made. The area

that is politically and scientifically still far in the future is the area

of atmospheric transfer, which in the case of petroleum remains an important

route by which petroleum hydrocarbons reach the oceans of the world.

What we need is hard data gathered with intercalibration in a system

whose design in time and space and quality controls are adequate to demand

the attention of decision makers. Otherwise they will continue to shy away

from decisions which would have a beneficial effect on the oceans. They will

continue to be preoccupied by the fact that a good piece of marsh is only

worth a thousand dollars.

So I think that the challenge is clear.

UNEP's role in this, at the international level, is to use the resources

that we have been given to catalyze new efforts and attract new resources. The Environment Fund, hundred million, sounds like a lot. But those of you

who know the scope of the program that confronts the world community realize

how terribly insignificant even this much money is relative to what needs to

be done. And this means of course, that the real work has to be done at the

national level. The role of the international agencies, particularly those

who have sponsored this meeting, is to help governments work together more

efficiently. The applicable lessons came out of the IGY and the exploration

of Antarctica, and they are practiced today in programs such as the World

Weather Watch, which have immediate practical, tangible results for rich and

poor around the world. The real work, of course, has to be done by you. We

are very happy that you're doing it. We hope that your results will come to us in the form of specific proposals. The expected results must be clearly

defined and the use of the data well understood. We will then see how, for our part, we can make the international system work a little bit faster, more energetically than it might without our help. Thank you very much.

NBS Spec. Publ. 409, Mar ine Pollution Monitoring (Petroleum) , Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg , Maryland, May 13-17, 1974

(Issued December 1974)

20
Pilot Project on Marine Pollution Monitoring

under the Framework of IGOSS

Dr. A. Tolkachev, Secretariat

Intergovernmental Oceanographic Commission, UNESCO

First of all, allow me on behalf of the Secretary of the Intergovernmental

Oceanographic Commission (IOC) to express our deep appreciation to the Government of the United States for hosting this Workshop and Symposium, for the

preparatory work that has been done and the excellent arrangements that have

been made. We wish to express our thanks and appreciation to the United

States Agencies that have been involved in the organization of the Workshop

and Symposium: the National Bureau of Standards, the National Oceanic and

Atmospheric Administration, and the Maritime Administration of the United

States Department of Commerce.

For several years the problem of marine pollution has been one of the

major problems under consideration and study by the IOC. A number of resolutions have been approved by IOC emphasizing the need to undertake specific

studies of various aspects in the field of marine pollution and recommending

specific action to achieve these goals. The marine pollution problem has

been outlined as one of the key problems in IOC's basic program of work

the Long-term and Expanded Programme of Oceanic Exploration and Research

(LEPOR) , approved by the IOC in 1969. The central role of IOC in promoting

and coordinating scientific programs and services in the field of marine

pollution was recognized by the United Nations Conference on the Human

Environment, Stockholm, June 1972.

At present, various aspects of this problem are under consideration,

and studies are being made by groups established by IOC or set up by other

international bodies to advise the Commission. In particular:

- the Group of Experts on the Scientific Aspects of Marine Pollution

(GESAMP) is a joint, specialized group consisting of experts nominated by the Inter-governmental Maritime Consultative Organization

(IMCO), the Food and Agriculture Organization of the United Nations

(FAO) , the United Nations Educational, Scientific and Cultural Organization (UNESCO), the WMO, the World Health Organization (WHO), the

International Atomic Energy Agency (IAEA) and the United Nations

which was established to provide advice to the sponsoring organizations and to IOC on desirable action to be followed in this field,

taking into account the latest state-of-the-art in matters relating

to the scientific aspects of marine pollution;

- the International Coordination Group (ICG) for the Global Investigation

of Pollution in the Marine Environment (GIPME) is responsible for

preparation of a comprehensive plan for implementation of GIPME, including specific recommendations for long-term coordination of the

program and the establishment of priorities for the projects contained

in the Plan;

21
- the IOC Working Committee for IGOSS, jointly with the WMO Executive

Committee Panel on Meteorological Aspects of Ocean Affairs (MAOA)

,

and the subsidiary bodies of the Working Committee—particularly the

Group of Experts on Oceanographic Research as it relates to IGOSS

(IRES) —are dealing with design, planning and development of the

marine pollution monitoring program;

- the IOC Working Committee on International Oceanographic Data Exchange

(lODE) , and particularly its ad_ hoc group on marine pollution data,

is responsible for development of procedures for exchange, storage,

archiving and retrieval of marine pollution data and information; and

- the Scientific Committee on Oceanographic Research (SCOR) , together

with other scientific advisory bodies to the Commission and the

International Council for the Exploration of the Sea (ICES) , has

established a Liaison Panel on marine research related to pollution

to correlate the activities of the subsidiary groups of the sponsoring organizations

.

It is obvious that all these studies and investigations are based on national activities, and success in this field on an international level

depends on the efforts undertaken by countries, national agencies, national

research institutions, universities, and individual scientists. Several

countries have already initiated such investigations in certain marine

areas on a national level or on an international level, especially in such

areas as the North Sea, the Baltic Sea, and the Mediterranean Sea.

It was recognized that, in order to review the state of the ocean and

its marine resources as regards pollution and the forecasting of long-term

trends, a worldwide system of monitoring of the constituents of marine pollution should be established. The need for the establishment of such a monitoring system was emphasized by the seventh session of the IOC and the

24th Session of the WMO Executive Committee; these governing bodies of IOC

and WMO decided that the Integrated Global Ocean Station System (IGOSS)

provides a suitable framework for the coordination of marine pollution monitoring activities in respect to physical and some chemical parameters. Furthermore, the United Nations Conference on the Human Environment, Stockholm,

June 1972, also recommended that the IOC, jointly with WMO and, as appropriate, in cooperation with other interested intergovernmental bodies, provide

the monitoring of marine pollution, preferably within the framework of IGOSS.

In light of the above decisions and recommendations, IGOSS planning and

subsidiary bodies recommended, as a first step in this direction, that a Pilot Project on Marine Pollution Monitoring be developed and that it should

focus on oil and dissolved petroleum constituents; they then prepared an Operational Plan for such a Pilot Project. Some of the experts sitting here

took an active part in its preparation: Dr. Ehrhardt (FRG) ; Dr. Levy (Canada);

Dr. Simonov (USSR); Dr. Zafiriou (USA); Dr. Zsolnay (Bermuda); R. Junghans

(USA); T. H. Thompson (Sweden); and others. This Plan is now before you as document lOC/WMO-IPLAN-II/ 3 . It was endorsed by the IOC Assembly at its

eighth session in November 1973 (Resolution VIII-20)

.

22
The basic purpose of the Pilot Project described in the Operational Plan

is to initiate the operational phase of a marine pollution monitoring program

on an international level, and on a large-scale basis, and to establish the

necessary organizational machinery to enable it to discharge its coordinating

role in a developing marine pollution monitoring program.

The selected vehicle for this project is petroleum derived oils since

it is possible to base a Pilot Project capable of involving nations with

widely varying degrees of expertise and capable of providing examples of the

type of organizational problems which will have to be overcome in any

coordinated exercise on marine pollution monitoring.

The Pilot Project will have to determine the state of oil pollution in

certain oceanic areas and to specify the areas and frequency of observations for a future oil monitoring system. Its further development will

enable us to evaluate the variability of pollution by oil in time and space

for operative purposes, and seasonal and year-to-year trends.

Internationally coordinated procedures will have to be developed during

the Pilot Project on sampling and on the preservation and analysis of water

samples, on formats for data reporting and exchange, and on the content of

products and services to be provided on an international level.

From the Operational Plan it can be seen that the Pilot Project will be

restricted initially to areas of the North Atlantic and adjacent seas and

waters around the African continent; these have been selected taking into

account the regions of offshore oil production, the main routes of oil transportation, and ocean current patterns.

For the Pilot Project, it is recommended that the following be monitored:

oil slicks and other floating pollutants; particulate residues or "tar balls";

and dissolved petroleum hydrocarbons in the surface water and in the water

column. Procedures for observations, sampling, and reporting of the above

parameters, as recommended for the Pilot Project are described in the

appendices to the Operational Plan. To evaluate the results of observations

and measurements, simultaneous observations of sea temperature, salinity,

dissolved oxygen, air temperature, wind, currents and waves are also recommended.

In preparing this Operational Plan, it was understood that initially all

the above measurements and observations would come from research vessels,

ocean weather ships, and suitable offshore platforms, especially with regard

to dissolved petroleum hydrocarbons. However, it is clear that, even at this

stage, other vessels suitably staffed and equipped should be involved in the

Project.

Recognizing that parts of this program are already underway, it is

nevertheless proposed that the Pilot Project begin on 1 June 1974 and run

for a 24-month period during which activities would be expected to intensify.

Periodic evaluation of the results of the Pilot Project will be undertaken

with the assistance of a Task Team consisting of individuals to be designated

by national coordinators for the Pilot Project, who will also be responsible

for preparation of a comprehensive report, to contain details of management

23
and scientific aspects. This report will be evaluated in conjunction with the

ICG for GIPME and recommendations will have to be made to the IOC Working

Committee for IGOSS and the WMO Executive Committee Panel on MAOA for the next

steps to be taken in marine pollution monitoring.

A global monitoring system has to be developed through progressive integration of existing national and regional systems, and monitoring programs

into an internationally coordinated program, and by encouraging their development in other countries on the basis of the experience. Therefore the IOC

and WMO Secretariats, in accordance with recommendations of the eighth session

of the IOC Assembly and the second session of IPLAN, requested Member States

of both bodies, by Joint Circular Letter No. 10, to provide details of their

interests and how they can contribute to the development and implementation

of the Pilot Project, and also to designate national coordinators. Up to

now, replies have been received from 26 countries, 16 of which expressed their

interest and willingness to participate in the Pilot Project namely: Argentina,

Canada, Egypt, the Federal Republic of Germany, Iceland, Indonesia, Ireland,

Japan, Korea, the Netherlands, Nigeria, Poland, Thailand, the United Kingdom,

the USA, the USSR, and Uruguay. Several other countries have designated

national coordinators and will shortly provide details of their participation

Australia, Belgium, France, Greece, and Norway. Details of national replies are presented to you as document lOC-WMO/MPMSW-I, the report of Task Team I for the Pilot Project.

The Joint lOC/WMO Planning Group for IGOSS recommended that a Workshop

and Symposium should be convened to develop further the necessary working

guidelines for the Pilot Project on Marine Pollution Monitoring, according to

the Plan developed in August 1973. This is one of the basic objectives of

this Symposium and Workshop, as outlined in the final program.

The Joint lOC/WMO Planning Group for IGOSS expected that the Workshop

would review the Operational Plan for the Pilot Project and provide recommended procedures and methodology for use by national coordinators in the

implementation at the national level of the operational programs for the Pilot

Project. Immediately thereafter, a meeting of the Task Team will be convened

here, with participation of some experts presently at this Symposium and

Workshop, to apply the results of the discussion to the Operational Plan and

to finalize it for presentation to partic' gating Member States.

To facilitate their work, several items and questions have been addressed

by the Joint Planning Group for IGOSS to the Workshop for consideration.

Allow me to point out the basic ones:

- procedures to be recommended for observing, sampling (including

preservation and analysis of samples) , and reporting of oil slicks

and other floating pollutants, particulate petroleum residues (tar

balls), and dissolved petroleum hydrocarbons;

- recommendations as to preparation of relevant manuals, guides, and

instructions on operational and technical procedures for use by

partic ipants;

24
- identification of further studies required for intercomparison and

intercalibration of sampling and analytical techniques and methodology,

including standards and intercomparison criteria; and

- recommendations as to new methods for monitoring of oil and dissolved

petroleum constituents, including the use of satellites, biological

indicators, and other parameters.

Here I wish to point out that the Group of Experts on Oceanographic

Research as it relates to IGOSS, at its fourth session (April 1974), stressed

the importance of such observations from voluntary observing ships and re- quested the Symposium and Workshop to consider the development of instruments

and methods simple and reliable enough for use on non-specialized ships without interfering with their normal operation, as well as development of

automated equipment for future use aboard those ships so that demands on the

ship's crew will be kept to a minimum.

With reference to the specification of recommended locations for monitoring and possible other ocean areas to be included in the Pilot Project, the

fourth session of IRES wished to draw your attention to the work undertaken

by Japan, described in the document entitled "Tar ball distribution in the

Pacific and Indian Oceans". IRES-IV requested the IOC Working Committee for

IGOSS to consider inclusion of the ocean areas around Japan in the Pilot

Project.

The IOC Working Committee for lODE has been requested to consider

standardization of methods and forms for reporting, dissemination, exchanging,

and archiving of information arising from the marine pollution monitoring

program. However, your views on this topic will also be of great value.

Proposals are solicited as to the types and forms of data that should

be included in the comprehensive final report on the Pilot Project, and for

identification of individuals to participate in drafting appropriate elements

of the above report.

A global monitoring program of any nature required wide participation

by Member States of the sponsoring organizations. Therefore participation

of developing countries in the Pilot Project will be of great importance and

value. We are very glad to note that a number of developing countries have

expressed their interest in participating in the Pilot Project and have sent

experts to this Symposium. It gives us a good opportunity to discuss and

identify their training, education, and assistance requirements, in order to

enable them to participate actively and, on the other hand, to indicate

availability and terms of technical assistance that can be provided in training, training aids, laboratory facilities, experts, and consultants. I wish

to note here that the Biological Laboratory at the Bermuda Biological Station

for Research has already offered to arrange a training course for experts

from the developing countries.

It should also be pointed out that the United Nations Environment Program has recognized the Pilot Project as an important step in developing a global monitoring system and has agreed to provide financial support for

25
its development. This will enable us to accelerate the planning and operational phases and, in particular, to assist developing countries in their

participation.

In conclusion, I wish you every success in your work during this week.

NBS Spec. Publ. 409, Marine Pollution, Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

26
Survey Analyses for Petroletim Derived Hydrocarbons In the Ocean

Sadaklyo Horl

Hydrographlc Department, Maritime Safety Agency, Japan

As one of the major terminals of the oil transportation routes In the

world, or as a country which greatly depends on fisheries activities, Japan

has, of necessity, been solicitous about the actual state of marine oil

pollution. In the most recent few years, some of the scientists who belong

to the government organizations have exerted their efforts on the quantitative measurement of petroleum-derived oil In the ocean, although they

have not yet achieved a sufficiently effective monitoring system at present.

Here I will describe some of their activities as a basis for further discussion

of marine oil pollution monitoring.

The Far Sea Fisheries Research Laboratory of Fisheries Agency has been

conducting larva sampling in the Indian and Pacific Oceans as part of the

tuna research project. Recently, particulate petroleum residues were

found to exist in the collected samples, and in 1971 K. Nasu of the laboratory, and his co-workers, started to investigate the distribution of these

residues in the oceans. Some 40 official ships, such as the fisheries

training ships or the fisheries research ships, have engaged in the project

and the same sampling method was employed for each ship. Larva nets of 1.4-

meter diameter and 4-meter length were towed for 15 minutes at a speed of

2 knots (traversing a distance of about 900 meters) . The amount of the

particulate residues were represented by an arbitrary scale for the sake of

convenience. Amounts were expressed as "Found" or "Remarkable" according

to whether the amount was less or more than 1/4 of the sample surface in

a 5-centimeter-dlameter bottle respectively. Fig. 1 shows the distribution

of the particulate residues in the ocean during the period from October 1971

to September 1972. According to K. Nasu and others, the particulate

residues are abundant in the marginal area of major ocean currents such as the

Kuroshio and the Indian South Equatorial Currents, and also along the major

oil transportation routes (as was expected)

.

The daily patrol for the illegal discharge of waste oil has been con- ducted by the patrol boats and aircraft of the Guard and Rescue Department

of the Maritime Safety Agency. Although the number of cases reported to the

Department does not seem to be increasing since 1972s there are still a considerable number of occurrences-more than 2000 annually. In 1971 and 1973

the Department conducted a survey of tar balls that had drifted to the coast

of Japanese islands, using its patrol boats, some 400 from local fisheries

cooperative associations, and some 650 of trusted monitors. According to

the survey, the greatest number of tar balls were found on the coasts of

the South-west Islands and on the Pacific coast (Fig. 2). In the same

period, the Department also conducted a sampling of tar balls by patrol boats

along 18 fixed routes in the open sea around Japan. The sampling routes were

chosen to take into account the shipping routes and the ocean current system.

The sampling method was as follows: nets of 0.75 millimeter meshes, 1-meter

diameter and 2-meter length were towed for some 500 meters at the speed of

2 to 3 knots, and the number of particles were simply counted. By this

27
survey, it was found that a considerable amount of particulate residues of

millimeter size are drifting in and around the Kuroshio current (Fig. 2)

and that there seems to be no significant difference in amount between

1971 and 1973.

The Hydrographic Department of the Maritime Safety Agency has been con- ducting chemical analyses of petroleum hydrocarbons in sea water to study

the present level of marine oil pollution, as part of the project monitoring

the sea around Japan, together with analyses of petroleum hydrocarbons in

the bottom sediments of major bays. The analysis was carried out by R. Higano of the Department and his co-workers, who took the saturated hydrocarbons (paraf f in-naphthene) as an indicator of the petroleum hydrocarbons

in the sea water or sediment. The distribution of petroleum hydrocarbons

obtained from their 1973 analysis are shown in Fig. 3. The chemical procedure employed in these analysis is as follows: Samples were condensed

after extraction with n-hexane, treated with alkali-alcohol solution,

charged to a column of activated silica gel and alumina, and diluted with

n-hexane. The paraf f in-naphthene in the first 20 ml was freed from n- hexane, weighed, and analyzed by a gas chroma tograph.

The same group analyzed surface, subsurface, and bottom (sediment)

samples, which were taken at each of some 18 stations in Tokyo Bay, to see how the discharged petroleum was distributed into these portions of

the Bay. In this study, the surface oil samples were scooped by a stainless steel net (30 mesh, 40 x 40 cm) and then dissolved into n-hexane,

and the bottom samples were collected by a Smith-Mclntyre Grab and treated

for one hour with alkali-alcohol solution in a steam bath before extraction.

According to their estimation 1 to lO""'- tons of petroleum were on the

surface of the Bay, 10^ tons in the water body and 10-^ tons in the bottom

surface layer of 10-cm thickness, and it was clear that the accumulation

of waste petroleum in the bottom sediment was very important, especially

in shallow waters.

In view of the above mentioned activities in Japan, it is considered

that many non-research ships and many men who are not marine sampling

specialists, must be involved for effective marine pollution monitoring

of wider areas; it is also clear that the techniques used must be the same

for each sampling, and the simpler the techniques, the better. To meet

such requirements, the techniques and instruments should be developed by

scientists. Further, to make monitoring more effective and to make data

interpretation easier, studies, such as on the calibration and accuracy

evaluation of the simplified techniques, and the oceanographic and meteorological studies of the monitoring areas, must also be done by scientists.

The scientific basis for such needed studies is expected to be discussed

during the Symposium.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Sjnnposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

28
Analysis Standards and Intercomparison of Data

Dr. Sidney

Deputy Assistant Secretary

Department of

R. Galler

for Environmental Affairs

Commerce , USA

Please consider this brief talk in the nature of a footnote rather than

anything larger since most of the topic that I am going to touch on today was discussed extensively yesterday and this morning. However, even though pouring oil on troubled waters is no longer fashionable today, I would like to

ruminate for a moment or two on the topic of analysis standards and the intercomparison of data, even at the risk of some repetition. I would like to

place this topic in a broader context in the hope of shedding a little more

light on a problem area that has been noted for the amount of heat it has

generated in the past.

The objective of this symposium is to discuss the status of marine pollution monitoring and the progress that is being made. Both aspects of this

symposium are parts of a larger area, the area of environmental protection.

I believe, however, that we cannot stop with environmental protection as the

ultimate goal; instead we need to perceive environmental protection and all

that it subsumes in an even larger context, as an important part of a larger

effort to improve the quality of life of all nations.

While environmental protection obviously is an essential requisite for

maintaining and enhancing the life support system for man, it is only one factor in the quality-of-life equation. In addition to the need to maintain

life itself, we need a sound economic basis to provide the goods and services

which yield the amenities of life, such as food, clothing, and shelter, adding

the dimension of quality to human existence. The balance between the need for

environmental protection, including marine pollution abatement and the need

to maintain a nation's economic health is a delicate one indeed, and the

maintenance of that balance depends to a large extent on our collective success

in identifying and correctly diagnosing pollution problems as well as in prescribing reliable, cost/effective corrective measures. Both diagnosis and

correction in turn depend heavily on our abilities to accurately measure and

monitor ambient environmental conditions and on our success in characterizing

marine pollutants and their sources.

The development of rational and justifiable pollution abatement regulations

must be based on three essential criteria. First, accurate and reliable scientific information and data in sufficient amounts to permit the development of

rational hypotheses and conclusions regarding the status of the environment;

second, the availability of demonstrably feasible monitoring and control technology; and third, the availability of a system for selecting cost/effective

options for solutions. However, in order to meet all three criteria, we must

develop standard measurement methodologies and practical means for the intercomparison of data.

This is especially important in attempting to cope with marine pollution,

not only because of the ubiquity of the oceanic environment, but because of

29
the practical impact of pollution controls on International commerce. The

degree of harmonization of international trade will depend to a large extent

on our success in gaining international acceptance of standard measurement

methodologies as well as in achieving intercomparability of environmental

measurement data on an international level.

The Stratton Commission Report to the President of the United States in

1969 stated that, "At present, there is a wealth of data within the nation

that is of limited value because of low confidence in the data quality or because the data came from diverse sources and are not comparable. This is

not only a national problem, but it is increasingly becoming an international

one." Today, of course, it is recognized as an international problem which

has fully matured. Fortunately, the numbers of laboratories and other institutions, both governmental and private, have increased, so we are in a better

position to cope with the problem than we were back in 1969.

For example, within the Department of Commerce, as you have undoubtedly

heard, there are two national facilities that have unique responsibilities

and capabilities for helping to assure data quality and comparability. One

is the National Bureau of Standards which is responsible for maintaining the

national standards of measurement for international agreements on standards

and for disseminating methods of achieving accuracy and comparability in

measurements wherever they are made. The other is the National Oceanographic

Instrumentation Center under the National Oceanographic and Atmospheric Administration which serves as a national focal point for oceanographic instrument

evaluation for recommended calibration procedures, for advice on instrument

performance needs and specifications, and for coordinating data as part of

intercomparison programs. Together, these laboratories and others like them

in other countries can do a great deal to help rectify the situation described

in the Stratton Report so succinctly, a situation which unfortunately still

exists. These laboratories are natural collaborators with advantages to each.

NBS furnishes expertise on the basic standards of measurements which can be

utilized by the NOIC. NOIC, in turn, provides a familiarity with real oceanographic measurement problems and thus becomes the interface between the National

Bureau of Standards and the oceanographic research community in assuring

traceability of oceanographic measurements to national and international standards among its other functions.

In the past, contact between these laboratories has been largely informal

in the sense that collaboration has been between professional scientists and

engineers in the two organizations. Hopefully, a more formal arrangement can

be worked out to facilitate the development of jointly funded programs.

Recently, an interagency committee was chartered by the Secretary of

Commerce to advise the NOIC on priority needs of Federal agencies engaged in

oceanographic measurements. NBS has membership on that committee. At present,

the Committee is working with NOIC on a policy statement, to be presented to

the Interagency Committee on Marine Sciences and Engineering, that will urge

all Federal agencies in the United States to work actively with the National

Oceanographic Instrumentation Center of NOAA to provide jointly accepted procedures for instrument performance evaluation and for instrument calibration

procedures and schedules. We hope that user agencies will actively participate

in data intercomparison programs as well.

30
Now, what about the rest of that quote from the Stratton Commission report,

"...the wealth of data that is of limited value because of low confidence in

the data quality." Here, again is an opportunity for the Department of Commerce,

through its National Bureau of Standards, to make vital contributions* Within

NBS , the Office of Standard Reference Data undertakes critical reviews of

measurements and data in fields of national priority.- These reviews can be

done either in-house or by outside experts through contracts. The product of

such a review is ordinarily a careful evaluation of an existing body of data,

raising it from a low to a high confidence level, resulting in the retrieval

of substantial (and often expensive) data from the archives for a more general,

practical use. It is my hope that NBS will be encouraged to develop high priority data evaluation programs pertinent to marine pollution research. Of

special interest today because of the growing availability of modeling techniques is the reliability assessment of the measured kinetic and transport

parameters that govern the movement of pollutants from sources to the oceans.

Let me conclude by suggesting that there are two basic high priority program areas in which progress will depend on the further development of international cooperation. One is the establishment of environmental base lines,

and two, the investigation of the biological effects of oceanic pollutants.

The great variety of marine and estuarine environments as well as the tremendous

diversity of biological species mandate the development of workable multinational instruments for scientific cooperation. Progress in these areas of

cooperation will depend as heavily on the utilization of intellectual resources

as well as on measurement and monitoring technology. Fortunately, the intellectual resources are available in most countries for the task at hand. Success can be achieved if scientists and technologists will organize well-coordinated international programs for attacking the measurement, monitoring, and

intercomparability of data problems. It is my sincere hope that this Symposium

signals the beginning of the attack.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

31

ih' Mil
i

j

1

]

I
Maritime Consideration of Oil Transportation

Mr. Howard F. Casey

Deputy Assistant Secretary for Maritime Affairs

Department of Commerce, USA

It is a pleasure to be with you today and I welcome this opportunity to

participate in this symposium on Marine Pollution Monitoring. I was particularly gratified to see that the program principals include 14 distinguished

ocean research scientists from other nations. For I believe that we all

will agree that pollution of the marine environment is an international

problem and can best be solved by preventive and remedial measures launched

on an international front.

While the pressures to institute marine pollution abatement measures

are particularly strong in the United States, it is also readily apparent

that there is a mounting universal demand that effective corrective actions

be taken to protect the marine environment.

Here in this country, all concerned parties recognize that the most

effective way to attack marine pollution problems is by international

regulations and standards. However, there is also a strong belief in some quarters that if such regulations are watered down, or subjected to un- acceptable ratification delays by other nations, the United States should

unilaterally impose stringent regulations to protect its coastal zones,

shorelines, and waterways from ship-generated pollution.

This is apparent from the fact that Congress has already enacted one law — the Ports and Waterways Safety Act of 1972 — calling for unilateral

pollution abatement measures which clearly reflected its dissatisfaction

with the lack of effective international standards. It should be noted,

however, that this law was enacted prior to the 1973 IMCO Convention which

focused on marine pollution abatement measures.

Before going into some of the specific factors and initiatives re- flected in our programs, I think it is important to provide this audience

with some perspective of the size of the American-flag tanker fleet in

relation to the world tanker fleet.

The American-flag fleet comprises 240 tankers aggregating 7.8 million

deadweight tons, equating to 5 percent of the number of tankers in the

world fleet, and less than 4 percent of the collective world tanker tonnage.

It also should be noted that foreign flag tankers transport about 95 percent

of this nation's oceanborne petroleum imports. Because most of our tankers

are of relatively small sizes, averaging only 32,500 dwt., they are generally uncompetitive in our foreign trade, and operate nearly exclusively

in our domestic trades and in the carriage of government-controlled grain

cargoes.

33
However, under the Merchant Marine Act of 1970, there is an ongoing shipbuilding program to bring about a reentry of American-flag tankers into our foreign trade. Since the enactment of this law, 30 crude and product

tankers for foreign trade operation have been ordered from American yards,

26 of which remain to be delivered. We also are building 27 additional

tankers for domestic operations. The total tonnage of these foreign trade

and domestic trade tankers is A. 5 million dwt., which is still a relatively

small percentage of the 219 million deadweight tons of tankers currently

under construction, or under contract, in the world's shipyards.

Our goals are to achieve the complete elimination of intentional

polluting discharges from ships by 1975 if possible, but certainly by the

end of the decade, and the minimization of accidental spills. We also

believe that these goals should be pursued through cost-effective measures

which will not impose discriminatory competitive burdens on the Americanflag fleet.

Our programs are influenced by in-house studies and initiatives dealing

with pollution prevention, as well as several laws enacted by the Congress

and existing and proposed international regulations to curtail shipgenerated pollution.

In terms of MarAd's (Maritime Administration) initiatives, since 1965,

all vessels built with construction-differential subsidy must conform with

the agency's Standard Specifications for Merchant Ship Construction. In

1971, as a result of mounting concerns about the marine environment.

Section 70 of these specifications, covering Pollution Abatement Systems and

Equipment, was revised to meet existing standards and certain anticipated

future national and international regulations. Section 70 has been

periodically updated to meet U.S. Coast Guard, EPA, and IMCO standards.

Among the compulsory requirements stipulated by Section 70 are an oilcontent meter to monitor ballast and bilge discharges, an oil-water

separator to process such discharges, tank size limitations, and a sewage

treatment plant.

Four laws in particular have had a major influence on our pollution

abatement programs:

(1) The National Environmental Policy Act of 1969

(2) The Water Quality Improvement Act of 1970

(3) The Federal Water Pollution Control Act, as Amended in 1972, and

(4) The Ports and Waterways Safety Act of 1972

The National Environmental Policy Act of 1969 directed all agencies of

the Federal government to utilize a systematic, interdisciplinary approach

in the planning and decision-making which may have an impact on man's

environment. In implementing this approach, the Act requires all Federal

34
agencies to prepare an environmental impact statement on proposals for

legislation or other major Federal actions that may significantly affect

the quality of the environment.

As a result of the shipbuilding program generated by the Merchant

Marine Act of 1970, MarAd has either issued, or is currently in the process

of issuing, several environmental impact statements which fulfill the

obligations of the National Environmental Policy Act.

The most significant and well-known of the MarAd environmental impact

statements is the one dealing with our subsidized tanker construction

program.

In accordance with a court-approved stipulation agreement dated

January 8, 1973, resulting from litigation action brought by the Environmental Defense Fund, Natural Resources Defense Council, Inc., and the

Center for Law and Social Policy, the Maritime Administration issued a Final Environmental Impact Statement on May 20, 1973. In addition, we

prepared an Economic Viability Analysis of eight different features which

the plaintiffs felt would make MarAd 's subsidized tanker program more

compatible with the environment.

These features included such items as twin propellers, and controllablepitch propellers for better vessel control, double bottoms and double sides

to prevent oil spills in case of accident, and flue-gas tank-inerting

systems to prevent explosions. Also analyzed were reductions in the size

of individual cargo tanks to minimize oil discharge in case of damage,

lateral thrusters - forward and aft - for better maneuverability, and

totally segregated clean-ballast systems to minimize oily ballast waste.

Subsequent to the issuance of the Final Environmental Impact Statement,

the Maritime Subsidy Board on August 30, 1973, issued a Final Opinion and

Order on the Tanker Construction Program. Some of the essential conclusions

and findings of this Subsidy Board Docket were:

(1) Present and future vessels receiving construction subsidy

shall be in strict compliance with MarAd 's tanker pollutionabatement specifications and a specification providing for

collision-avoidance radar;

(2) All tankers in excess of 100,000 dwt. receiving government

aid shall contain inert gas systems in the absence of a satisfactory reduction in tank sizes;

(3) MarAd will continue to participate in, and support, IMCO and

U.S. Coast Guard efforts to devise major anti-pollution design

and equipment features for tankers and to incorporate into

government-aided contracts such anti-pollution features

established by the 1973 IMCO Marine Pollution Conference and/

or Coast Guard regulations;

35
(4) MarAd training programs will include anti-pollution

training manuals and course materials for tank vessel

operation; and

(5) MarAd will intensify its research and development

activities to improve technology in combating marine

pollution with respect to the operations of oilcarrying vessels.

Other environmental impact statements that MarAd is involved in are:

(1) An environmental impact statement on the MarAd Chemical

Carrier Program. A draft statement on this subject was

issued on March 15, 1974;

(2) An environmental impact statement on the MarAd Title

XI Program Vessels Engaged in Offshore Oil and Gas

Drilling Operations. The draft statement on this

program will be issued early this summer;

(3) A Proposed Shore Facility for Treatment and Disposal of

Ship Generated Oily Water Wastes. The Final Environmental

Impact Statement for the facility was issued on November 27, 1973:

(4) An environmental impact statement on our Nuclear Ship

Program which is currently being developed under contract

to the NUS Corporation.

To return to the U.S. laws which impact on marine pollution, the Water

Quality Improvement Act of 1970, enacted in April of that year, stipulates

that it is the policy of the United States that there should be no discharges

of oil into the navigable waters of the United States, upon adjoining

shorelines, or into the waters of the contiguous zone which cause a visible

sheen or discoloration of the water. (A visible sheen informally is defined

as 10-20 ppm of oil.)

The Federal Water Pollution Control Act, as amended in 1972, declares

the national goal of "complete elimination of discharge of pollutants in

our navigable waters by 1985 and an interim goal of water quality providing

for the protection of marine resources, wildlife, and recreation by

July 1, 1983." The Act provides for the imposition of financial liability

for the discharge of pollutants from vessels or shoreside facilities. It

also authorizes the EPA to set standards and promulgate regulations for the

performance of marine sanitation devices aboard vessels.

Finally, the law which may have the greatest impact on the Tanker

Construction Program is the Ports and Waterways Safety Act of 1972. Under

this law, the Coast Guard was authorized to insure the safe movement of

vessels in congested port areas by controlling vessel traffic. It also

authorized the Coast Guard to promulgate rules and regulations for tankers

entering U.S. waters, setting forth minimum standards of design and con- struction of tank vessels for the purpose of protecting the marine environ36
ment. Such rules shall also set standards designed to improve vessel

maneuvering and stopping ability and to otherwise reduce the possibility

of cargo loss in the event of accidents, and to reduce pollution by normal

vessel operations, such as deballasting, cargo handling, and other activities.

While such rules and regulations were promulgated, they were held in

abeyance to ascertain IMCO's consideration of recommendations for international standards last fall. It is understood that the Coast Guard will

issue construction and operating standards for U.S. flag coastwise tank

vessels which will become effective on July 1 of this year.

MarAd has played an increasingly significant role in supporting U.S.

international efforts by its participation in IMCO activities and by

developing back-up economic and technical studies in support of the U.S.

Anti-Oil Spill policy initiated by President Nixon in his message to the

Congress of May 20, 1970. This message called for effective multilateral

action by international bodies, such as IMCO, to prescribe international

standards for the construction and operation of tankers.

The U.S. Anti-Oil Spill Program was given further impetus by then

Secretary of Transportation Volpe's pronouncement of "zero discharges" of

oil by mid-decade. The NATO/CCMS Conference Resolution, subsequently

adopted as the goal of the 1973 IMCO Marine Pollution Conference, fell short

of the original U.S. position, but called for work to start at once to

achieve by 1975, if possible, but not later than the end of the decade, the

elimination of intentional pollution of the seas by discharges of oil and

oily wastes.

Prior to the 1973 IMCO Marine Pollution Conference, the original

concept of "zero discharge" meant no discharge, or zero parts per million

(ppm) . However, this was considered by industry as unrealistic and un- attainable under present day technology.

The 1973 IMCO Marine Pollution Convention replaced the "zero discharge"

concept with "zero polluting discharge," which was defined as 15 ppm, or no visible traces, of oil. The more realistic approach taken by the 1973

Convention gave us a little more room to work with. As one can recognize,

however, the cost to achieve 15 ppm is still substantial and, therefore,

it is felt that additional research is needed to confirm the need for such

high standards.

Nonetheless, the requirements adopted by the 1973 IMCO convention are considered by the U.S. to be, in the most part, cost-effective and realistic.

Besides establishing the "no discharge" zone of 50 miles from land, the

Convention required new tankers to be designed with segregated ballast

capabilities and all existing tankers to be fitted with a Load-On-Top

System for handling oily ballast and tank washings.

In addition, a new IMCO committee has been established, the Marine

Environment Protection Committee. This Committee has been given the

responsibility for handling all future marine pollution issues for IMCO.

It is the intent of the Committee to shorten the traditionally laborious

37
task of amending and issuing new international pollution control standards.

IMCO has also recognized the importance of the development of scientific

information, such as that being discussed at this symposium and workshop.

Resolution 12 of the 1973 IMCO Marine Pollution Conference specifically

calls for the "Development of Scientific Information on Water Quality

Criteria."

MarAd is firmly committed to the policy that strong and effective

pollution control regulations can go a long way towards protecting the

marine environment. However, before rigid standards can be established, we believe a definitive basis must be developed which indicates the need for

such standards. This is particularly true when high pollution control

standards require costly and sometimes unrealistic construction and design

requirements for vessels.

It is the hope of the Maritime Administration that this symposium and

workshop will help establish and formalize the techniques and standards

required to determine the actual fate and effect of oil spills or discharges into the marine environment. Such standards are needed to establish

a baseline of data that will be the basis for realistic requirements.

With the development of baseline data and uniform measuring techniques

and procedures, effective control devices can then be designed and manufactured to protect the marine environment from vessel source pollution.

In this area, MarAd has initiated two studies, discussed during the course of this sjmiposium, which are designed to develop a data base for

future practices, and regulations regarding the control of marine pollution.

The basic objective of these two projects is to establish a body of

hard knowledge and basic data in order to determine, with some degree of

scientific precision, the level of oil in the open oceans and the amount of

oil contained in ship discharges considered to be harmless to the marine

environment. We feel that the establishment of baseline information will

permit a more rational approach to the formulation of realistic and meaningful standards for permissible oil discharges from ships.

Our first program, initially set up with ESSO Research and Engineering

in June 1972, was designed to collect and analyze ocean samples to determine

background hydrocarbon levels in the ocean waters. Data developed from this

study showed that extremely low hydrocarbon concentrations existed in

surface and subsurface waters.

Subsequent to the completion of this particular project, ESSO Research

and Engineering has required and received additional funding from NOAA,

with funding support from MarAd, to extend its ocean sampling program in the

Pacific Ocean, concentrating on the Port Valdez to West Coast routes.

Another program which has been co-sponsored by the same three agencies

sponsoring this workshop, NOAA, NBS, and MarAd, is the Fate and Effects

Study on the Scientific Aspects of Oil Discharges in the Marine Environment.

38
This program, although somewhat hindered by funding cutbacks, originally

called for a study to establish the fate and effects of oil discharges on

the marine environment and to use this information to form the basis for the

establishment of meaningful standards. Several of the papers given here

have been the direct result of this project.

It is apparent that the work of this group to develop techniques for the

monitoring of marine pollution is very pertinent to the goals of the Maritime

Administration, as well as to other agencies and organizations represented

at the workshop. As indicated by the wide range of papers from the various

ateas of interest, i.e., government, industry, and academia this subject is

undergoing a very thorough research effort.

I am hopeful that the activities of this sjmposium will result in the

development of working guidelines for marine pollution monitoring that will

significantly advance the objective of producing oil tanker equipment and

systems that will effectively protect the marine environment at a reasonable

cost.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

39

Marine Pollution Data Archiving and Exchange

Mr. Richard M. Morse

Environmental Data Service, NOAA

In 1961, at its formative session, the Intergovernmental Oceanographic

Commission of UNESCO established its first standing working group, the

Working Group on International Oceanographic Data Exchange (lODE). Only

a year earlier. United States ocean scientists had appealed successfully to

their National Academy of Science and to the Legislative and Executive

Branches of Government for the establishment of a national oceanographic

data center. I cite these two examples to indicate that only ocean scientists

and coordinators of ocean science programs are concerned with effective

exchange of oceanic data. In keeping with this philosophy, I will speak

to you today on the subject of effective international exchange of marine

pollution data.

In 1970, the Working Committee, lODE, at its fifth session, considered

the first and second reports of the Group of Experts on the Scientific

Aspects of Marine Pollution (GESAMP) and their expressed desire for the

establishment of arrangements by which all data pertaining to marine

pollution could be suitably stored in the world or specialized data centers.

The Group of Experts on the Long Term Scientific Policy and Planning

proposed a program for the Global Investigation of Pollution in the Marine

Environment (GIPME) and a data information and management system to

accompany that program. Following this, the chairman of GESAMP addressed

correspondence to the chairman of the Working Group lODE, expressing his

concern for the capabilities of the national and world data centers to

adequately archive and exchange marine pollution data. Added to these concerns, was the concern of the pre-Stockholm Conference Meetings of the

Intergovernmental Working Group on Marine Pollution (London 1971) and the

Intergovernmental Working Group on Monitoring and Surveillance (Geneva 1971)

as related to data and information exchange. Late in 1971 and prior to

the Stockholm Conference these considerations resulted, at the Sixth

Session of lODE, in the establishment of an a^ hoc Group on Marine Pollution

Data. The terms of reference of this group include:

"a. The ad hoc Group will identify types of data which should be included routinely in the category of marine pollution data for international

exchange, and the feasibility for automatic processing of such data. Other

pollution data and relevant information not amenable for international

exchange should be identified and proposals made for an adequate referral

system for them. Recognizing that there are problems in the lack of

standardization in some categories of Biarlne pollution data, the Group should

study and recommend the ways in which such data could be made available for

international exchange; and

b. The ad hoc Group should recommend a means b}^ v/hich marine pollution

data, identified as to the foregoing, already stored in various archives

can be appraised as to their availability for uses such as baseline studies

and trend analyses. Sources of such data would include various regional,

41
national, international and other archival and research institutes. The

Group should also take into account the potential role of national coor- dinators for marine data management."

There is a common tendency for scientists who come together to talk

about data and data exchange to spend considerable time and effort speaking

to the problems and interests of their science before they can settle down

to addressing the matter of data exchange. This tendency is completely

understandable and, of course, provides the necessary perspective in which

the matter of data exchange must be clearly viev/ed; that is, if effective

exchange is to be arranged, the full cooperation of the scientist is a vital matter.

It was in this vein that the U. S. member of the lODE ad hoc Group

on Marine Pollution Data, supported by the Director of the U. S. National

Oceanographic Data Center and the National Science Foundation's Office of

the International Decade of Ocean Exploration, called a workshop of

prominent analytical marine chemists to discuss these matters in July 1972.

The results of this workshop were incorporated into the report of the

ad hoc Group as presented to the lODE at its Seventh Session, United Nations,

New York, 1973.

In brief, the Workshop agreed that free and effective, rapid exchange

of marine pollution data, including micro-contaminant chemistry, was possible only in those instances v/here there were internationally accepted

standards for sampling, measuring, calibrating, etc. Only in such cases could the measured value of the concentration of a chemical constituent

stand alone as a numerical value having meaning to other scientists and users of the data. Only then could such numbers be usefully placed into

a central data bank, merged, and then used to produce summary products such

as horizontal and vertical distributions, trend analyses, or other statistical

products. The Workshop also agreed that, at the present time, there were no chemical measurements in the ocean that enjoyed this status, (with the

possible exception of salinity and nutrient chemistry, for which reasonably

well-accepted analytical techniques and standards permit the meaningful

direct exchange of numerical values on chemical constituent concentrations,

that waiting several years for the assemblage of data and subsequent

publication of selected data was an alternative which could be improved upon.

Even so, the scientific literature will probably remain the only viable

alternative for promulgation of research data from those experiments that are at the fringe of analytical technique or instrumentation development.

But it was further suggested that, in most cases, it would be possible to

improve upon these alternatives by extensive documentation of the basic data

set. Documentation as to sampling material and technique, shipboard fixation

methodology, the time delays between sampling and fixation, identification

of analytical methods, and instrumentation including shipboard and laboratory

standards were but a few of the dozens of documentation items suggested by the

Workshop. Thus, a numerical data set accompanied by such documentation would

permit any of a variety of secondary users, scientists, managers, and citizens,

to evaluate and draw their own conclusions as to the usefulness of a particular data set for a particular purpose.

42
The strength of this approach becomes apparent when one realizes that

similar documentatioti, accompanying not only data sets but simple inventories

of data, can provide for archiving of inventories in addition to or in place

of archiving of the actual data. Thus, two additional advantages accrue.

First, such documented inventories of marine chemistry data may be automated

readily, be made fully searchable, and be extremely useful as a data referral

tool. This is specific and documented referral, thus reserving the time and

cost of full exchange to those instances where the usefulness of such an ex- change is evaluated in advance. Second, such documented inventories may

readily serve as a means by which earlier files of unpublished or only

partially published observational data may be brought to light in an organized fashion available for the review of today's concerned ocean community,

and evaluated for possible selective accessioning into a baseline file.

Such an approach has been recommended by the lODE jad hoc Group on Marine

Pollution Data and approved by the parent Working Committee lODE and the

Intergovernmental Oceanographic Commission.

Subsequently, in January of 1974, national coordinators for International

Oceanographic Data Exchange were asked to contact their nation's scientists

and program managers involved in marine pollution research and monitoring

to implement a pilot system of documented inventories. This early pilot

effort may use any system meeting the goals of a documented or second-level

inventory. The Report of Observations /Samples Collected on Oceanographic

Programs (ROSCOP) is considered a first-level inventory, not a second-level

inventory such as we suggest here, but both the lOC/SCOR ROMBI form (that is.

Report of Marine Biological Investigations) which contains an extensive

pollution section, and the U. S. Environmental Data Index (ENDEX) inventory

systems, which have been introduced into the TODE, have potentials for this

use. Such inventories would be accompanied would any actual data transmission, by documentation which would include specialized information such

as that recommended in the first report of the ad_ hoc Group on Marine

Pollution Data, and, hopefully, any additional documentation that may be

suggested by this group in the workshop which follows later this week.

No reports are yet back from the National Coordinators for International

Oceanographic Data Exchange, but I am aware of several countries where this

matter is presently being considered in relation to the developing IGOSS

Marine Pollution Monitoring Pilot Project. To assist in this effort, I,

and several of my international colleagues, will join the pollution scientists

and managers participating in the workshop convening tomorrow.

There are two other ad hoc Groups of the lODE Working Committee who share

our interests in these matters. These are the ad hoc Group on Format

Development and the ad hoc Group on IGOSS Data Archiving and Exchange. The

former group is concerned primarily with establishing optimum formats for

fully processed and carefully validated data sets which will form the long

term permanent archive. The latter group is concerned primarily with procedures and formats for archiving and exchange of IGOSS data which have

either been transmitted over the international telecommunications system,

or for which re-dissemination or data products are short term services.

There has been insufficient advance in the work of my ad hoc Group to permit

us to make any specific recommendations to the lODE format development group.

43
However, we have continuing close liaison with the work of both of these

ad hoc groups. In this regard, the deliberations and considerations of

this joint meeting of the IOC and WMO scientists will serve as a sound

basis upon which to advance the work' of all three lODE subsidiary bodies.

For those of you remaining to participate in the workshop which

immediately follows this symposium, I actively solicit your constructive

support of the present and future work of these groups. For the longer term,

I further solicit your active support and continued cooperation through your

national coordinators for the IGOSS Marine Pollution Monitoring Pilot Project,

your national coordinator for IGOSS and your national coordinator for International Oceanographic Data Exchange. We are privileged to have with us to

participate in the workshop, the Director of the Federal Republic of Germany's

National Oceanographic Data Center who is his nation's coordinator for both

International Exchange of Oceanographic Data and for the Pilot Project; Mr.

Jaquiam Ros of Spain who is a member of my sid hoc Group on Marine Pollution

Data and his nation's coordinator for the IGOSS Marine Pollution Monitoring

Pilot Project; Mr. Thomas Winterfeld, Chairman of the lODE ad hoc Group on IGOSS Data Archiving and Exchange; and Mr. Robert Ochinero, the U. S.

National Coordinator for International Oceanographic Data Exchange and

Director of the U. S. National Oceanographic Data Center. I hope you will

indeed assist us in this aspect of the IGOSS Marine Pollution Monitoring

Pilot Project.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

44
Biological Environmental Effects

Mr. Maurice E. Stansby

Director, Environmental Conservation Division

Northwest Fisheries Center, National Marine Fisheries Service, NOAA

At the discussion this morning, there was quite a bit of intermingling

of matters concerning both monitoring and effects of contaminants. I would

like to make it clear that I agree with Dr. Ehrhardt that effects are a separate matter, something that is quite distinct from the monitoring. Nevertheless, I feel quite strongly that there must be a continuous dialogue between

people carrying out the research on effects and the people who are planning

and carrying out the monitoring activities. I will have more to say about

this before I am finished, but first I want to talk about our program on effects at our Northwest Fisheries Center.

This program got underway shortly after NOAA was established as an agency

in 1970. At that time, we had had some work going on along this line, particularly by Bob Clark, in connection with monitoring the content of petroleum

hydrocarbons in marine organisms in Puget Sound, but about two and a half

years ago, we set up an environmental conservation division to which we brought

Bob Clark and his program and to which I brought from the utilization side of

the old Bureau of Commercial Fisheries a group of chemists. This became the

first nucleus of our environmental conservation activities. We soon were

supplied with other scientists with different disciplinary backgrounds, such

as biologists, physiologists, geneticists, and microbiologists. Today we have

a staff of about 30 scientists who are able to undertake work on the different

aspects of our program from different points of view. We have the program

arranged in three units so we can approach things from different standpoints.

In the first unit, which consists mostly of chemists, we are looking at

how the contaminants enter the fish, either through the food or through the

water, and how the contaminants distribute themselves around the body of the

fish; how they interact; the mechanisms by which they bring about harm at

vulnerable sites, and then something about how they might be metabolized so that they are eliminated by the fish's defense mechanism.

In the second unit, we are looking at the behavior of fish, mainly from

a physiological standpoint. We are more concerned with long term chronic

effects than just the lethal effects. We are looking at such things as the

effects of contaminants upon the disease resistance of fish, the effects upon

sense organs, and other types of effects.

In the third unit, we are looking at how fish behave in their natural

environment. We have several field stations where we are able to compare the

results of some of our laboratory investigations with what goes on in the

natural habitat.

We are undertaking this work to ascertain long term chronic effects

rather than lethal effects. I would like to tell you about one project in

which the technique being used is a little bit different than those being

45
used in any other part of the world with which I am familiar. This project

is being carried out by Dr. Roubal of our staff and it involves something

called spin labeling. It is being used to look at what goes on at the membrane

level and subcellular parts of fish. We have chosen this because it is at

the membranes that many of the enzymes and other types of activity which can be interferred with by contaminants that enter the fish operate. Spin labeling

is a new technique that was developed at Stanford University about five years

ago. Primarily, it has been used in the field of medical research; we are

among the first to use it in marine science. It is a very simple technique

and yet one which gives considerably more information than the analogous

radioisotopic tracer techniques because it shows not only the presence of the

tracer, but also in what kind of an environment it is located. It is especially useful to be able to look at what is happening at subcellular levels

because we can tell whether the contaminants go to the surface of membranes,

whether they penetrate the membranes, or whether they are associated with

lipids, proteins, or other factors. The technique has been used in our studies so far only for examining how salmon pick up and distribute contaminants obtained through their food. Later we will extend the use of this

technique to other aspects and other species. My discussion here will be

restricted to salmon and their ingestion of hydrocarbons through their food.

In a general way, this work is carried out very simply by feeding separate hydrocarbons to the salmon for different experiments. Then all we have

to do is examine the part of the fish that we are interested in. We have

be6n using spinal cords because we feel that contaminants have the greatest

potential for harm when they enter the neural systems. We dip the spinal

cords in a solution of the label, then place the specimen in the instrument,

and immediately get a chart that gives us all the information that we need

to know.

We are using several types of labels (Fig. 1) which also have been used

in medical research. Each has a nitrous oxide group that contains the free

radical that sends back the information. They are attached to different

types of compounds that will penetrate membranes to different distances from

the surface, either remaining on the surface or going just beneath the surface or to the center.

Figure 2 shows such a label penetrating at the upper right portion into

the center of a membrane. The center of the membrane is a sort of a fatty,

lipid material. Figure 3 shows the type of curves we get. The top curve

is the spectrum for a label without any contaminant present; this label is

directed into the interior of the membrane. The curve below shows the type

of curve that appears when an aliphatic hydrocarbon has been fed to fish and

then is placed into the instrument. The two curves tell us that the aliphatic

type of hydrocarbon has gone to the center of the membrane. If, however, we

had used a fish that had been fed with aromatics, we would have gotten a curve identical to the one shown at the top, indicating that aromatics do not

go to the center of the membrane.

In Figure 4, we have a labeled membrane in which the label is directed

to the surface of the membrane. Here, if the fish has been consuming aro- matics, we get the different type of curve (shown at the bottom) indicating

that the aromatics are at the surface of the membrane, but if we had used

46
fish fed aliphatic hydrocarbons, there would have been no change, showing

that the aliphatics were not at the surface, but at the center.

In further studies using radioisotopic tracers, we have shown that the

aliphatics which occur at the center of a membrane can be gotten rid of

quite rapidly, but not completely. Within about a month's time, the values

fall to about 10 percent of their original value, but after this period of

time, they continue steady for many months for as long as our experiment has

lasted. The aromatics, on the other hand, which occur at the surface of the

membrane, disappear almost at once; within two or three days they have reached

undetectable limits. We believe this is because they are in the presence of

enzymes which can very rapidly purge them.

This is a very rapid technique. We expect to expand its use to other

species of fish and to hydrocarbons which enter the fish not only through the

food but also through the water.

We have other programs too numerous to mention here. These include

examining the effects of hydrocarbons upon the sense organs of fish. Some of

our preliminary findings are that there seems to be an interference with the

olfaction activity, but not with the lateral line in fish.

We are, at present, planning an expansion of our activities by a cooperative program with Environmental Research Laboratories, another agency

within NOAA that has a facility at Seattle, and we hope, perhaps by the next

fiscal year, to be carrying out a considerably larger program in cooperation

with that agency.

Now, I would like to come back to this matter of cooperation and dialogue between people who are carrying out the monitoring programs and those

who are carrying out the type of activities that we engage in at Seattle.

About three years ago, I attended a meeting during which I listened to the

discussions about monitoring programs to be carried out. Finally, I spoke

about how we should also consider the matter of effects upon the fish of the

things that were being monitored. I was told that the first thing that had

to be done was to find out where the contaminants went in the water, and that

this would take about 10 years, and that I should come back in 10 years and

then we could discuss what needed to be done with respect to the effects.

Now, I felt very strongly then as I do now, that this is not the way to

approach the matter; that monitoring is not an end in itself. It has to be

done, keeping in mind that the monitored contaminants may be harmful to the

environment. In the National Marine Fisheries Service, we are concerned with

what happens to the fish. Therefore, we are concerned about whether enough

of the ideas of the people working on biological effects are being introduced

into the thinking of the people planning the monitoring. I noticed yesterday

that, in one of the discussions on collection of surface waters, they were

talking about taking samples to a depth of one meter. I feel that this is a good example where, from the standpoint of the biochemists and the biologists

and the biologists and the people looking at the effects of contaminants, we

should know much more about what happens in the first two or three centimeters because, under some circumstances, eggs of fish are floating at the

surface, and at the surface there is much higher concentration of contami47
nants than there is at a depth of one meter. So, it is this type of information I think we need to pass back and forth between these two groups so that the work that is done will be much more meaningful.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

48

S
Maritime Considerations

Mr. John J. Nachtsheim

Assistant Administrator for Operations

Maritime Administration

Department of Commerce, USA

International Convention for Prevention of Pollution from Ships

After two years of concentrated effort, the International Convention for

the Prevention of Pollution from Ships was adopted by the IMCO Conference on Marine Pollution held in London, October 8 to November 2, 1973. This Conference,

attended by 665 delegates from 79 countries, U.N. Agencies and intergovernmental

and non-government organizations adopted the 1973 Convention, consisting of

twenty Articles and five Technical Annexes. In addition, the Convention

adopted the Protocol Relating to Intervention on the High Seas in Cases of

Casualties Involving Marine Pollution by Substances other than Oil. The

Convention further adopted twenty-six Recommendations and Resolutions.

This was a true landmark achievement in responsible intergovernmental

cooperation and a significant step forward in achieving high pollution control

standards on an international basis. The 1973 Convention will enter into

force 12 months after it has been ratified by not less than 15 States, the

combined merchant fleets of which constitute not less than 50% of the gross

tonnage of the world's merchant shipping. Upon its entry into force, the

present Convention will supersede the 1954 International Convention for the

Prevention of Pollution of the Sea by Oil and the 1962, 1969 and 1971 amendments thereto.

The 1973 Convention will be forwarded to the U.N. Conference on the Law

of the Sea to be convened next month so that it can be taken into account by

the Law of the Sea Conference.

The main objective of the 1973 Pollution Conference was "... the

achievement by 1975, if possible, but certainly by the end of the decade, of

the complete elimination of the willful and intentional pollution of the seas by oil, and noxious substances other than oil, and the minimization of

accidental spills ..."

To a large degree if the provisions of the Convention are implemented

on a worldwide basis, that objective has a good chance of being achieved.

There are, however, some difficulties that must be overcome if the provisions

are to be effective. First, and quite naturally, the Convention must come

into force and be complied with and enforced to achieve the desired reduction

in pollution. Secondly, the provisions must be feasible of achievement.

While, for the most part, the provisions adopted by the 1973 Convention are considered cost-effective and realistic, there may be certain provisions of

the Convention which will be difficult to achieve. I would like to focus my

discussion on two examples which I believe fit this category. Further, I believe the examples I have selected in this regard are close to your interests.

One of these relates to construction standards, the other to operational discharge standards. Following each of these I would like to discuss what the

Maritime Administration is doing to overcome these difficulties.

49
Maritime Administration Role in Pollution Prevention

The main thrust of the Maritime Administration's (MarAd) program is in

the prevention of oil pollution through cost effective measures which will

maintain the competitive position of the U.S. merchant fleet. MarAd 's program is based on the achievement of National goals in coordination with other

government agencies and with the commercial organizations with which the agency

deals. MarAd 's main governmental coordination concerns the U.S. Coast Guard,

the Environmental Protection Agency, and the Council on Environmental Quality.

The U.S. Coast Guard, through IMCO and its subsidiary activities, such as the

Maritime Safety Committee and the newly established Marine Environment Protection Committee has effectively spearheaded this combined interagency effort.

Since bulk ships, including tankers, are now part of the MarAd program since

their inclusion by the 1970 Merchant Marine Act, MarAd has played an increasing role in supporting this effort and will continue to do so in the future.

The MarAd Standard Specifications for Cargo Ship Construction provide

guidance for merchant ship designers preparing detailed ship specifications,

especially for ships to be built with Government Construction Differential

Subsidy. First prepared in 1965, the Standard Specifications were updated in

19 72. Currently the Agency is preparing a totally new Standard Specification

for tankers. As a result of the increased emphasis placed on measures to

control ship generated pollution. Section 70 - "Pollution Abatement Systems

and Equipment" of the Standard Specifications was revised in its entirety in

March 1971, to consolidate all pollution abatement features of cargo and

tanker construction and operation to control oil, sewage and air pollution.

Until recently. Section 70 has been advisory in nature. However, as a result

of action taken by the Maritime Subsidy Board in August 1973 (Docket A-75)

,

Section 70 is now a mandatory requirement for all tankers built under the

MarAd Program. Section 70 is currently under review to ascertain if any new

requirements are needed. The provisions of the 19 73 Marine Pollution Convention, for example, are being carefully studied to determine what changes

to Section 70 will be required to meet that Convention. As part of this

review, we have noted certain difficulties and this brings us back to my

previous point that two provisions, one a construction standard and one an operational discharge standard, will be difficult to achieve. These are the

operational discharge standard dealing with oil content meters and oily water

separators and the construction standard for segregated ballast.

Oil Content Meters and Otly Water Separators

Marine operations make up about 49% of the known total estimated annual

oil pollution of the oceans. By marine operations I mean the movement of

tankers, tank barges and other vessels. Not included in this are offshore

drilling operations or other non-marine transportation operations such as refineries and petrochemical plants, industrial machinery and highway motor

vehicles which make up the remainder of the known oil pollution. The known

total for all the above does not include oil contributed by recreational boats,

hydrocarbon fallout and natural seepage which, by some estimates, is as large

as the known pollution. In all, this would make the marine operations con- tribution smaller proportionately but by no means insignificant. Quite the

contrary; marine operations accounted for an estimated total of 2.3 million

50
metric tons of oil pollution worldwide in the year 1970. More than half of

this is from tankers. Almost a million tons are from all other vessels and

the remainder is from tank barges. The known causes of pollution are usually

characterized as intentional and accidental. Accidental causes include

collisions, groundings, rammings , breakdowns, fires, explosions and structural

failures. The term "intentional" gives an unfortunate connotation, but basically includes causes such as those resulting principally from vessel operating

practices. These are tank deballasting, tank cleaning, bilge pumping, terminal

operations and bunkering spills. Operational discharge accounts for more

pollution than does accidental by a ratio of more than 4 to 1, although most

of the spectacular publicity on pollution from vessels results from the latter.

While these figures are large, they would be much larger had not tanker

operators taken voluntary measures, beginning in the early 1960's, to minimize

dumping of oil to the sea. This was accomplished by adopting the procedure

known as Load-on-Top (LOT)

Tankers designed without exclusive segregated ballast tanks will normally

take sufficient sea water in their cargo tanks after discharging the cargo to

insure proper propeller immersion and to provide good handling and sea-keeping

characteristics and to maintain the required stability conditions. The ballast

water that is put directly into the empty cargo tanks after the cargo is discharged comes into contact and mixes with the oil that adhered to the tank

surfaces or remained at the suction mouths and cargo piping system after cargo

discharge. This oily ballast must be disposed of in some way prior to arrival

at the loading port, or retained on board and discharged to a shore reception

facility. When the oily ballast is disposed of at sea, the empty cargo tanks

are then filled with sea water which can be disposed of into the harbor at the

oil terminal loading port.

This type of ballast handling operation, commonly referred to as "uncontrolled ballast discharge," causes all of the oil residue in the tank washings

and approximately 15% of the oil residue from the tanks which were initially

ballasted to be pumped overboard. The amount of oil discharged to the sea depends on the amount of oil that remains in the tanks after discharge at the

unloading port. This is referred to as "clingage," and is considered to

average 0.3% of the cargo capacity for crude oil and 0.08% for light oils.

Recognizing that the intentional pollution resulting from the uncontrolled

discharge to the sea of the oily ballast water and tank washings represented

a major source of ship-related oil discharges, the oil companies instituted

the LOT ballasting procedure. On tankers using this procedure, the oil in

the dirty ballast and tank washings is not pumped directly overboard but

instead is retained on board and diverted to a slop tank.

When employing the LOT method, tankers on their return ballast voyage

take on sea water in several of the cargo tanks in sufficient quantity to

maintain required stability conditions, while the remaining empty cargo tanks are cleaned by butterworthing or similar tank cleaning process. All the tank

washings are then pumped out of the cleaned tanks and transferred to the slop

tank. After the tank cleaning is completed, fresh sea water is pumped into

the washed tanks, which now contain clean ballast water. At the same time,

the oily sea water in the cargo tanks which were used for ballasting is permitted

51
to stand until the oil residue in the tanks has gravitated to the top. The

decanted water in these tanks is now discharged overboard until the oil/water

interface is reached. The oily slops from the dirty ballast tanks are then

pumped to the slop tanks. At this point, the oil in the slops is given time

to separate from the water by gravitating to the top. The decanted water

under the oil in the slop tank is carefully pumped into the sea.

Upon arrival at the loading port, the clean ballast water is discharged

and only oil in the slop tank remains. The new cargo is then taken on board,

and is loaded "on top" of the remaining oil in the slop tank. The effectiveness

of LOT depends on the length of voyage, type of oil, and weather, all of which

affect the settling out and gravitating of the oil. In addition, effectiveness

relates to crew training and skill in the operation. The practice of employing LOT has reduced this source of pollution by 90%. The result has been the

elimination of over 3,000,000 tons of oil pollution per year. It is significant to note that this saving alone, which was accomplished voluntarily, ex- ceeds the present total known oil pollution from all marine operations.

To further improve LOT, work must be done to improve oil/water separators,

interface detectors and oil content meters. The 1973 Convention requires that

all tankers be fitted with an approved oil discharge monitoring and control

system. For enforcement purposes, this system must be provided with a recording device to produce a continuous record of the discharge in liters per

nautical mile and total quantity discharged or of the oil content and rate of

discharge. It must come into operation when there is any discharge of effluent

into the sea and ensure that any discharge of oily mixture is stopped automatically when the instantaneous rate of discharge of oil exceeds that permitted

by the Convention. In this connection, it might be pointed out that for 30

inch lines such as those used in very large tankers, a so-called quick acting

valve requires as much as one to two minutes to close in order not to burst

pipes nor damage valves or pumps. Tankers must also be provided with effective

detectors for a rapid and accurate determination of the oil-water interface

in slop tanks. The fact is that equipment to meet the Convention's standards

exceeds today's state of the art for that equipment. With regard to oily water

separators low flow separators (50-100 gpm) needed for cargo systems are not

workable. In the case of oil content meters, the meter has to be recalibrated

when different types of oils flow through the meter and the error of the equipment generally exceeds the 15 ppm accuracy required.

Installation of monitoring systems is required in existing tankers three

years after entry into force of the Convention and in new tankers, upon entry

into force. This provision permits time for development of monitoring devices

suitable for the various grades of oil and for orderly retrofitting of existing tankers. Since the 1973 Convention applies to all grades of oil, persistent

and non-persistent, i.e., crude oil and light refined, the Convention permits

each Administration to waive compliance of the requirement for monitoring of

light refined products until such time as this equipment is available. The

Convention prescribes that IMCO will annually review the availability of such

equipment

.

52
While it can be expected that industry will initiate or accelerate development work to meet these requirements in new equipments, the Maritime Administration is undertaking an extensive R&D program to assist.

At the National Maritime Research Center (NMRC) in Galveston, Texas,

designs are underway for an Oil/Water Separator Test Loop which will greatly

increase the progress on the testing of oily water separation systems interface detectors; oil content meters, and related hardware for handling bilge

and ballast waste, tank cleaning wastes, and waste from LOT procedures.

The Test Loop will not only allow the testing and evaluation of oil/water

separators but also will provide better control of testing parameters. Upon

completion of the Test Loop, NMRC-Galveston will act as a certification agency

for the Maritime Administration for oil/water separator systems.

To improve LOT effectiveness, MarAd has already obtained concentration

profiles for dirty ballast, clean ballast, and slop tanks for several different

crude oils. The profiles were correlated with settling time, oil density, and

washing time for clean ballast. The data has been analyzed and is being

applied to determine optimum ballast handling procedures and any additional

treatment requirements

Developed data indicates that separation of oil/water mixtures within

slop tanks contain high concentrations of oil. In this area, different design

concepts are being investigated for slop tanks and their internal structures

to improve their use as gravity separators. In addition to basic tank geometry,

vortex emulsion breakers, baffles, inlet and outlet configurations, and transfer procedures are being studied.

Therefore with the impetus that the 19 73 Convention has provided, it is

hoped that industry's efforts, augmented by an effective MarAd R&D program

will overcome the current technological inability to meet this provision of

the 1973 Convention.

Segregated Ballast

The 1973 Convention makes mandatory, in all new tankers of over 70,000

tons deadweight, contracted for on or after January 1, 1976, or delivered on

or after January 1, 1980, the requirement that they be fitted with segregated

ballast tanks sufficient in capacity to provide adequate operating draft without the need to carry ballast water in cargo tanks. During the ballast voyage,

in any ballast condition, including the condition of light ship plus segregated

ballast only, which condition excludes stores or fuel as part of the ship

weight, the ship's draft and trim must meet the following requirements:

(a) Draft (amidship) = 2.0 + 0.02L, in meters.

(b) The trim by the stern not to exceed 0.015L.

(c) The draft at the after perpendicular must be

sufficient to obtain full immersion of the propeller(s)

Ballast water may only be carried in oil tanks in weather conditions so severe that, in the opinion of the master, it is essential for the safety of

53
the ship to carry additional ballast water in oil tanks. This additional

ballast water must be processed and discharged in accordnace with the operational discharge requirements of the Convention.

This segregated ballast requirement is not technologically difficult to

achieve. Rather, its difficulty lies in the fact that it will have an economic

impact on tanker design, construction and operation because it will require

the utilization of large dead, volumes which cannot assist in the earning

capacity of the ship. In this connection it should be noted that world order

books show a large backlog of orders for new tankers to be delivered prior to

1980. This backlog almost equals the world's present operational tanker

deadweight capacity. In addition there are still almost two years to contract

for additional tanker tonnage which could be delivered before the end of the

decade. Therefore tanker tonnage exempt from the segregated ballast requirement will be sufficient to handle much of the world's crude oil transportation

needs at least through the 1980 's and well into the 1990 's.

Still, because this requirement has such economic consequences and because the adoption of the requirement preceded the present world concern for

energy, it is important to assure that its impact is mitigated to the maximum

practical degree before that point in time when it does become a controlling

design requirement.

The impact of this provision on the designs currently under construction

in the MarAd Tanker Construction Program was investigated. It shows that the

current National Steel and Shipbuilding Company's tankers of 89,700 DWT would

lose 6,950 tons of cargo deadweight, (7.7%). The Seatrain Corp. tanker of

225,000 DWT would lose 14,700 tons of cargo deadweight (6.5%). The Bethlehem

Shipbuilding Co. tanker of 265,000 DWT would lose 25,400 tons of cargo deadweight (9.6%). This amount of lost carrying and earning capacity is a price

that will have to be paid to meet the current requirements. New designs

specifically aimed at optimizing this requirement could not appreciably improve these figures either.

The level of segregated ballast that was adopted by the 1973 Convention

was the result of a compromise of differing views. Maritime Administration

studies to date indicate that the minimum levels of ballast required for safe,

inballast operation, are significantly lower than the present 1973 Convention

requirements. Since ships have taken on more ballast than is generally con- sidered necessary because there was no penalty associated with doing so, ships

have really not had operational experience of any significant amount in the

lighter displacement conditions.

Model tests sponsored by MarAd at Stevens Institute and subsequent com- puter analyses resulted in minimum levels of ballast that are significantly

lower than the IMCO requirements . The Oil Companies International Marine

Forum (OCIMF) also demonstrated with full scale test voyages that the present

levels of ballasting can be safely reduced by a large percentage. The Netherland's model work and Norwegian study of current practice also point to the

possibility of acceptable levels lower than the current formulation.

The recent increase in bunker prices could have a significant effect on discouraging overballasting as well, in that operators are looking to reduce

54
resistance and save fuel. The realization of the high costs of segregated

ballast could also result in a concentrated worldwide effort at reducing the

average levels of ballasted displacement. All of these factors point to

potential future reductions in ballasting levels and the need for international

effort at promoting a uniform reduction in these ballast levels.

MarAd therefore has proposed to IMCO, through appropriate channels, that

a research program with the following goals and elements be pursued:

(a) Identify immediate improvements needed in the IMCO

segregated ballast formulation in view of present

designs and ballasting practices.

1. Investigate impact of present formulation on current designs.

2. Survey present ballasting practice of different

bulk operators on 1,000 DWT to 500,000 DWT vessels.

(b) Determine minimum levels of ballast necessary for safe

ship operations.

1. Conduct analytic and experimental studies of

structural response, comfort and other limiting

considerations resulting from lightly ballasted

conditions.

2. Obtain full scale test voyage statistics at lower

levels of ballast reviewing damages, repairs, crew

comfort, time saved, fuel saved, etc.

3. Conduct careful full scale correlation runs with two

differently sized tankers (90,000 DWT and 250,000 DWT)

measuring pitch, slamming, propeller racing and deck

wetness frequencies along with sea conditions and

structural strains in the bow area.

4. Correlate full scale runs with model tests and

computer runs

.

5. Perform maneuvering studies to determine the

difficulty of maneuvering in and at low ballasted

displacements

.

6. Perform model testing and computer analyses to

determine the lowest necessary ballasting levels for

safe ship operation.

(c) Determine the incentives necessary to induce masters to

take advantage of the ability to operate tankers safely

at lower ballast drafts.

1. Investigate training, change in policy and other

factors necessary to encourage ship masters to

operate with less ballast. Consider the potential

savings resulting from higher costs and the added

cost of segregated ballast features as a guide to

limits on financial incentives

.

55
This action is in full keeping with the spirit of the 1973 Convention

inasmuch as Resolution 8 of the Convention recommends that "IMCO take appropriate action to consider these ballast draft requirements, . . . and to

examine them with a view to determining whether any improvement is required . .

Conclusion

While the adoption of the 1973 Convention was a truly significant step

in raising pollution standards, it should not be considered the final solution

to the prevention of global marine pollution. Because of the rapid amendment

procedures of the new Convention permitting changes in the regulations as a result of developments or new technology such as the data developed at this

Symposium and Workshop, international pollution standards will continue to

be updated. This process should also be materially improved as a result of

the establishment of the new Marine Environmental Protection Committee under

IMCO. In addition, there is much to be done to assure that this Convention

comes into force. There is also much to be done to upgrade our capabilities

in the area of detection and enforcement to assure that the provisions of the

Convention when they do come in force, are not hollow expressions of good

intentions only. Nor should those provisions be unnecessarily onerous out of

doubt or ignorance that they create distrust and abuse. There is still much

to be done.

Scientific exploration must be continued and the fruits of that effort

must be engineered into practical achievement. MarAd is firmly committed to

the policy that strong and effective pollution control regulations can go a long way toward protecting the marine environment. However, before rigid

standards can be established, we believe a definitive basis must be developed

which indicates the need for such standards. This is particularly true when

high pollution control standards require costly and sometimes unrealistic

construction and design requirements for vessels. The work you have done and

hopefully will continue to do can help a great deal in establishing the proper standards. I hope I've given you a little insight into some of the ship

problems so that you will be encouraged to continue to work in your fields

toward our mutual goals

.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Syroposiu;:! and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

56
Regulatory Functions

Mr. T. A. Wastler

Chief, Marine Protection Branch

U. S. Environmental Protection Agency

Regulatory programs In marine environment usually exist either to prevent

over-exploltatlon of a commercial resource or to protect a part of the environment from damage or destruction. International agreements for the protection

of some specific types of marine resources have existed In one form or another

for a number of years and recently, more general agreements directed toward

protection of the general marine environment have been agreed to or are approaching agreement.

The International Ocean Dumping Convention was ratified by the United

States on April 29, 1974. This country was the 6th nation to ratify the

Convention which comes into force when 15 nations have ratified it. This

Convention regulates the dumping of waste materials into the ocean from

barges and other floating craft. Several highly toxic bio-accumulative or otherwise damaging waste constituents or materials are prohibited as other

than trace contaminants. Mercury and its compounds, cadmium and its compounds,

organo-halogens and oils and greases are such materials. Other waste materials may be dumped under permit by the nation from which they are transported.

You have heard about the provisions of the IMCO Convention which is in the

final stages of approval. This Convention, as was mentioned, deals with the

operating discharges from ships such as tank cleaning and cargo related

dumping or discharges. In addition to these Conventions, negotiations are beginning to establish an International basis for the regulation of deep sea mineral resources and for regulation of land based sources of pollution.

No international convention for the regulation of the environment can be

effective without an active and efficient program to monitor the environment

in terms of what is being regulated and what effects are being controlled.

The marine environment, particularly the open oceans, has been primarily the

working place of the research community; and the development of an integrated

monitoring program to serve regulatory needs is just beginning. The IGOSS

project on Marine Pollution Monitoring is a major step in that direction.

In discussing how regulatory programs need and can use monitoring data,

I would like to cover three general topics: First, the kind of information

needed for regulatory purposes; second, the present situation with regard to

the availability of such Information; and, third, the types of developments

we would like to see started.

The first question is - what kind of information do we actually need for

the implementation of an adequate regulatory program? Whether the source of

the pollutants is from outfalls, from direct ocean dumping, or from the

operating discharges from vessels, the type of information needed from the

environment Itself can be grouped into four categories:

1) We need to know what materials are being discharged and are likely

to be discharged Into the ocean. This, of course, is not the type of

57
information that is acquired in a marine monitoring program itself, but it is

essential to have such information in order to know what observations should

be made on the marine environment. From a knowledge of the types and

distributions of waste sources, the sampling requirements for marine monitoring programs can then be developed.

2) From a knowledge of waste types and sources, the locations of probable impact from these sources in the ocean, particularly in the near shore

areas, can be developed and the appropriate parameters to identify specific

pollutants and their impacts can be incorporated into a marine monitoring

program.

3) From a regulatory standpoint, in terms of monitoring the oceanic

environment, those parameters of importance would be persistent synthetic or natural organic materials not normally found in the ocean, and trace materials,

particularly metals of a toxic and bio-accumulative nature. The impacts of

these materials would be very difficult to characterize from a monitoring

standpoint since they would probably appear as changes in the viability or appearance or non-appearance of various forms of life in certain areas. A

monitoring program to characterize these types of impacts probably would have

to consist of broad scale biological surveys in certain geographic areas rather than monitoring at point locations. Information is needed also on water movement and circulation so that the probable areas of impact of

various forms of waste can be traced from their sources.

4) An effective system for collecting and disseminating these types of

information is required together with a mechanism for identifying adverse

trends before critical or irreversible conditions are reached.

The next point I wish to mention is where we are now in terms of

monitoring needed to support regulatory activities. This can be summarized

very briefly by simply stating that we do not have any oceanic monitoring

program effective enough to support a regulatory function. The ratification

of the Ocean Dumping Convention by each signatory nation will require a commitment by that nation to conduct monitoring activities to determine the

effects of waste dumped under the permits that it issues. Actual monitoring

efforts so far are minimal. In the United States, we do not yet have an effective ocean monitoring program, although we anticipate that such a program will be initiated during this calendar year. Even then, however, our ability to anticipate and determine effects is extremely limited. In terms

of oil and petroleum derivatives in general, which are the primary concern

of this symposium, our basic regulation and criterion as to a trace amount

is that quantity which will make a visible sheen on the surface. This approach

may be useful in determining the impact of sewage sludges and industrial

wastes dumped from barges or out-falls, but it does not lend itself to control of materials such as tar balls and floating films which may be observed

on the surface of the ocean, but for which no visible source of pollution

can be found. What then would we like to see in the way of development in

marine monitoring from the standpoint of the regulatory program? First, we

need a development in technology and technique which would permit us to measure on an automatic and remote basis the concentration and distribution

of floating materials, such as tar balls and films on the ocean. Second, we

58
would like to see analytical development in the analysis of such materials so that it would be possible to trace them back to their sources. Third, we

would like to see the establishment of key biological or chemical parameters

which should give us an idea of the health of the various parts of the

ocean before critical conditions are reached. Fourth, we would like to see

the development of a mechanism for the rapid collection and dissemination of

this information to the appropriate international and national regulatory

organizations

.

^ In summary, I would like to point out that the development of international

agreements and conventions for the control of marine pollution are useless

without the parallel development of the mechanisms and technology for the

technical implementation of these agreements. When we talk about international

agreement to control marine pollution, it must be in the context of what kinds

of scientific and technical programs are required to carry out the spirit and

intent of the convention. In the case of the pollution of the world's oceans,

we must think clearly in terms of what we need to know about that ocean on

a regular basis and make sure that whatever monitoring programs are developed

and implemented are done with full knowledge of the regulatory coimnitments of

the various nations in mind and the technical requirements for meeting these

commitments

.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

59
s
Regulatory Functions as Related to Vessel

Construction and Operation

Captain S. A. Wallace

Chief, Marine Environment Protection Division

United States Coast Guard

I am here today representing Rear Admiral Benkert, the Chief of the

Marine Environment and Systems of the United States Coast Guard. He had a schedule conflict which did not permit him to speak to you as planned. He

particularly likes to speak to scientists, so I know he regrets not being

here. In examining the list of attendees, one or two things occurred to me

that may raise questions. If we have time for questions, I will be glad to answer at the conclusion of my talk.

I serve as U. S. Chairman of the Marine Pollution from Shipping Working

Group under the bilateral agreement between the United States and the Soviet

Union for protection of the environment. In the Soviet Union, this Group is

under the auspices of the Ministry of Merchant Marine.

I am the scientific leader of the Working Group on Marine Pollution

pursuant to the U. S. -France bilateral agreement on oceanography. I do have

a program colleague in the room, Jean Claude Mourlon, who is from CNEXO in

Paris

I had been deeply involved in the 1973 Marine Pollution Conference of

which so much has been said today, participating in four preparatory sessions

in the conference itself and in the Marine Environment Protection Committee

which was newly formed in IMCO after the Conference; and I did serve as the

U. S. spokesman at the Conference in Committee 2, which was responsible,

among other things, for developing Annex I which governs oil. This Convention

is the product of our many months of labor, and I am prepared to refer to it

if anyone has a question. I had a colleague on the U. S. side who is present

today: Captain George Steinman of MARAD.

Now the application of monitoring, in the sense that you are using the

word in this symposium, is in its very early stages of evolution in serving

the needs of regulatory programs in the United States. We do have research

and development efforts underway. We audit the development of effective

monitoring in related fields, but we have yet to apply monitoring to any

significant degree in our regulatory programs.

I am going to discuss briefly our legal mandates and I ask that you view

these mandates as constituting discrete functions, many of which lend themselves to monitoring applications, and for the benefit of our colleagues from

other countries, I must say that, after examining the regulatory schemes effective in those countries, our system here in the United States is analogous.

We have statutes; we have agencies responsible for implementing those statutes; and most of these agencies publish regulations. The Federal Water

Pollution Control Act, Section 311, which has aptly been termed an act within

an act, is our chief mandate; that is, the Coast Guard's chief mandate, in

oil and hazardous substances pollution abatement. Under that section of

61
the Act, we are responsible for transportation-related facilities. The EPA

has responsibility for regulating non-transportation-r elated facilities.

The Coast Guard has issued its regulations for vessels and for terminals;

these regulations will be effective the first of July 1974. We are presently,

together with other agencies in the U. S. Department of Transportation, developing regulations for transportation-related facilities in other modes of

transportation—rail, highway, etc. There is a $5,000 civil penalty for

violation of these regulations and the agency that promulgates the particular regulation is responsible for assessing the penalty.

With regard to the occurrence of discharges, the Coast Guard is designated as the appropriate agency for notification, a function which, through

regulation, we now share with EPA. Failure to notify by the person in charge

of the vessel or facility responsible for a spill will make that person subject to a $10,000 criminal fine or one year in jail or both. The discharge

makes the discharges subject to a "no-fault" penalty. The polluter, if it can be established through substantial proof, is subject to up to $5,000

in civil penalty. This program is administered by the Coast Guard, either

through our own investigations, through EPA's investigations, or through

investigations by any of the 50 states.

We have a function we call "response", which is synon5raious with cleanup. The Coast Guard is responsible for response to spills in coastal waters,

the Great Lakes, harbors, estuaries, etc. The EPA has the inland area. We

work with them in developing contingency plans.

The Coast Guard manages a pollution fund that is used to finance the

clean-up of spills where the polluter either fails to do so, or does not

do so properly in the opinion of the Federal official on the scene.

We maintain a National Strike Force, composed of three teams, Atlantic,

Gulf, and Pacific, located on those coasts. These are highly trained, wellequipped teams, with quick air transportation at their disposal, who are dedicated to responding to spills and available to anyone who needs them,

not just the Coast Guard. This is a national strike force. If the EPA calls

for them, they respond immediately, just as they would to a Coast Guard

District Commander. The Coast Guard also maintains a national response center on behalf of several agencies which make up what is called the National

Response Team. This team is responsible for planning on a national level

for developing the procedures to be followed when spills occur. Also, this

team can be convened in the case of a major spill with severe ecological or political ramifications.

Now, in my view, we need monitoring in the response area to serve several purposes: To help us detect spills; to establish the dimensions of the

spill; to assess when our clean-up is effective; and to serve as evidence in

enforcement proceedings against the polluter.

The Ports and Waterways Safety Act was mentioned earlier; the Ocean

Dumping Act, and the Marine Protection Research and Sanctuaries Act have

also been discussed. The Coast Guard has several roles here. Essentially,

we enforce the permits issued by EPA or the Corps of Engineers, depending on

62
what substance is to be dumped. We ensure that dumping is carried out in

accordance with the permit. We have a surveillance and monitoring (in the

non-scientific sense) role in this. We do have authority to issue regulations.

However, we do not intend to do so unless a clear need arises. A pattern of

permits presently exists which makes regulation-making on our part unnecessary.

With respect to research and monitoring, we will be working with NOAA and EPA

in assessing effects of dumping.

The Oil Pollution Act of 1961 in the United States implements the 1954

Oil Pollution Convention. We have said much about the 1973 Convention. We

have expended a great deal of effort, blood, sweat, and tears toward developing that Convention, but what we have today internationally is the 1954

Convention. Generally, this prohibits discharges within prohibited zones around continental land masses—this means within 50 to 100 miles of land

depending on what land mass we are speaking of. It establishes a specific

oil content for water discharge by tanker or other vessel operations to

100 ppm, and requires an oil record book be kept by each tanker. I might

emphasize that this Convention applies only to oil and only to a portion

of the family of oils —the so-called persistent oils or black oils. There

are two sets of amendments worthy of note: The 1969 amendments to the 1954

Convention and the 1971 amendments. The 1971 amendment establishes tank size

limitations. The 1969 amendments generally prohibit discharges within 50

miles of land; state that the discharge may not exceed l/15000th of the cargo

capacity of the tanker (or 100 ppm for other vessels); and state that the instantaneous rate of discharge shall be less than 60 liters per mile with the

tanker underway. We do not know when these amendments will come into force.

Some 18 nations have ratified the 1969 amendments, including the United States,

and some 28 are required to ratify to bring the amendments into force. It

is, I suppose, conceivable that the 1973 Convention will come into force

before the 1969 amendments. I will answer questions about the 1973 Convention

if there are any questions stemming either from my discussion or those preceding.

With regard to the use of monitoring data to assist with regulatory function, the Coast Guard does not consider itself a primary user of raw data,

and perhaps "raw data" is a poor term to use in this scientific forum, but

please blame the ignorance of the lajnnan. The Coast Guard will and does

assist other agencies who have a responsibility in this area in gathering

data. We feel strongly that ultimately, the data must be used to determine

the efficiency of the national program. We are engaged in research and development efforts to improve our detection capability. We have in operation

sensor-equipped aircraft with what we call off-the-shelf sensors —ultra-violet

and infrared—and we are developing a much more sophisticated system for

future use although we cannot determine that it will be practical and costeffective until we put it into operation. We are also considering on-site

sensors in busy harbors and sea lanes which we would hope can help us detect

violations of our environmental standards.

Monitoring for a regulatory purpose through scientific means and procedures is a procedure which is yet to be exploited in our regulatory operations. We are certainly open to suggestions and recommendations and, to

the extent that monitoring programs mean money, we are open to persuasive

arguments related to cost-effectiveness, and budget justification, one of

63
those nasty things that we are up against at least once a year. Ultimately,

we will need scientific means to determine whether our regulatory efforts are bearing fruit —which means cleaner water—and where our efforts are shown to

be ineffective, we will need these means to determine how these regulatory

efforts can be reshaped to meet the mandate of national pollution policy. Mr.

Stansby remarked that monitoring is not an end in itself; neither are regulations.

Our goal is effective protection of the marine environment for the ultimate good

of mankind. We will do the regulating and, given the tools, we will do the

monitoring to achieve this goal.

DISCUSSION

Question ; Do we have specifications for detergents used for responding to oil

spills?

Wallace ; It is the policy of the United States —through the responsible agency

which in this instance is EPA—that we not use chemicals except in a very

limited way in combatting oil spills. There are several approved herding agents we may use. We do not use sinking agents. We do not use any agents that will

apread the oil or disperse it into the water except in an emergency. An on- scene coordinator does have the authority, where safety of life and property

is involved, to use dispersing agents. But, as a rule, such use is not allowed

in the United States. I realize that many other countries feel differently.

We do have a considerable amount of information about this , and our research

and development is continuing with the hope that we will be able to show that

such agents can be used without harming the environment. Some chemicals are more harmful to the environment—and I am stating this, not as an expert, but

according to EPA—than is the oil which they would disperse. If I can provide you with any useful information on these chemicals, I will be happy to do

so.

Question : Is it reasonable to have international standards for pollution control in view of the lack of international standards for measurement? (Questionei

referred to a previous paper submitted by Mr. Richard Morse, NOAA)

Wallace ; Well, I cannot speak for Mr. Morse. I would think though, that he

was speaking of scientific measurements, perhaps finely calibrated measurements,

which can be proven in a laboratory. I think that at the 1973 Marine Pollution

Conference (which incidentally was an international conference, not an "IMCO"

Conference) the point was made that this is a fine, but important distinction.

At that conference, at least so far as the technical standards and regulations

are concerned, these points were developed by people who knew the sea and

ships. I am not talking about what went on in Committee I and the articles

that had to do with international law in its broader reaches, but to technical

standards. And we believe this is an entirely defensible position which can

be shown, which can be demonstrated, which can be measured. And here I would

disagree with one previous speaker with regard to the state-of-the-art. With

very little stretching, current techniques are adequate, if not today, at the

very least by 1976, which as you probably are aware is the date which fixes

the rules for new ships . I think we are probably talking about two different

64
kinds of standards. I would certainly yield to Dick Morse, but I know what

kind of standards we were talking about in Conference Committees, and while

we did apply a great amount of scientific work particularly with bulk chemicals, we used tried and true time-tested nautical measures of oil when we dealt with

the Annex I. I do not personally believe there is an anomaly here.

*****

The following telegram sent by Dr. N. J. Campbell, Chairman of the Working

Committee for IGOSS, was read. Dr. Campbell was unable to attend because of

health reasons.

"Sincerely regret my inability to attend and participate in

the deliberations of your S5rmposium and Workshop; however,

I would like to express my best wishes for success to all

those countries and participants taking part. Much depends

on the outcome of your decisions and work which will have far

reaching effects on setting the future stage for marine

pollution monitoring research and investigations by the IOC.

I am certain your approach to these problems will be followed

in many other fora since it cannot help but be judged as a breakthrough in the progress and development of such work,

and in the capability of IGOSS to respond to the needs of such

things as the Stockholm Resolutions and of Member States of the

IOC. We will all be looking forward to launching the Pilot

Project on Marine Pollution Monitoring as soon as possible.

Best wishes and good success."

N. J. Campbell, Chairman W/C IGOSS

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

65

Concluding Remarks

Dr. Thomas S. Austin

Director, Environmental Data Service, NOAA

When the Chairman asked me if I would give the so-called "wrap-up," I indicated that I would be happy to speak on the philosophy and concepts of

data management. He very tactfully suggested that the wrap-up does not concern concepts of data management, it concerns what we hope the workshop will

achieve in the next few days. It's a little like the scientist who had

worked for long years on earthworms and as he was standing in for his orals

the first question was, "Mr. Doe, would you discuss elephants." So he thought

for a moment because he didn't know anything about elephants and he said,

"Well, the elephant is an animal with a trunk and a tail and the tail is

round like an earthworm. Now you take earthworms and ..." So that's what

I propose to do. I'm going to discuss the elephant and then I'm going to ease into earthworms before I'm through.

I think this is most interesting and appropriate because I think it's

a major step forward—the Pilot Project which will lead to, I'm sure, a much

more viable and global concept. One only has to remember that approximately

100 years from last year, the Challenger embarked on the first of the major

round-the-world oceanographic cruises. To many of you, the name Challenger , subsequently coupled with names like the Meteor , Lomanosov , Atlantis , Discovery , Umitaki Maru , Jean Charcot—the list goes on and on—highlights the fact that

studies of the oceans on a global basis are truly of international concern.

As a result of exploration and description, they are now beginning to analyze

mechanisms and rates of change, and this all leads to learning to predict.

Now, certainly the processes that have been identified are many. The thermal

characteristics of the ocean—I have a note here, apologies to the interpreters if I describe it as the internal thermal commotion in the ocean—the

chemical balance or imbalance which is one of the aspects that you have

addressed yourselves to the past 3 days and will address yourselves to in even greater detail the rest of the week and early next week. Surface and

subsurface interactions of the sinking at the Poles, the return through upwelling, and circulation on macro, meso, and micro scales.

Now, what we have been doing—we, collectively as oceanographers of

nations—is establishing baselines, probably motivated by the innate curiosity of man and the desire to learn the relationships between ocean phenomena

and weather, transportation, food, and recreation.

Certainly we have come to realize that no one nation has the resources

to do the task that must be done. No one nation would have the resources to

adequately, particularly in a synoptic concept, look at the North Atlantic

or the North Pacific, South Atlantic, South Pacific, or Indian Ocean. There

must be international cooperation—nations working together. The examples

are many and I shall not dwell on them now, but the Intergovernmental Oceanographic Commission, which has now had about 1 decade of life, had its con- ception to bring together the scientists of the nations of the world that

were interested and are interested in the oceans.

67
IGOSS was the first of the major surface service aspects of the IOC.

The first project was the BATHY Pilot Project, which was a multination effort

to bring together with the cooperation of meteorological organizations and

communications capabilities information primarily through the use of the

Bathythermograph, that would permit biweekly analyses of the temperature

conditions in the North Atlantic. The pilot project was a success, and certainly it is hoped that many other nations than those in the pilot project

will become involved in this concept.

Man's activities have led to recognizable and, as you have learned during

the past 3 days, to a degree measurable impacts on his environment. I like

to use the word "inadvertent" because I am confident, as a member of the

generation that probably caused a lot of the recognizable and measurable

changes to the environment, that these were inadvertent. Regrettably, it

has not always been official. It certainly was the recognition of this that

led the IGOSS System to the development of the concept for and the development

of the marine pollution monitoring program. A decision was made carefully

and intentionally that the first phase, the operational phase of the Pilot

Project, would speak only to petroleum hydrocarbons. This particular form

of a contaminant, a pollutant, was chosen because it seemed to hold out the

greatest chance for success in terms of the objectives of the Pilot Project.

It had a visual aspect—tar balls and oil slicks. You have heard a number

of papers that suggest there have been significant analytical breakthroughs,

advances, in the general area of chemistry of the hydrocarbons. It would

allow monitoring pretty well on a global basis among areas where one may

expect a reasonable high to low level of pollution. I hate to use the word

high, but certainly comparatively speaking, the measurable levels should be

related to those areas of the world's oceans where, hopefully and conceivably,

there would be a much lower level.

If I may have the first slide. You have already seen this slide which

will be used by the people in the workshop in terms of their first review of

suggested areas for changes, if such are in order. The Sjnnposium in the last

3 days has essentially laid the groundwork, exposed those who are going to be

involved in the workshop to the relative levels of contemporary technology so that they make reasonably sound decisions as to what the pilot project should

encompass. What is proposed is also under consideration within the United

Nations Environment Program, the EARTHWATCH and the related Global Environmental

Monitoring System—"an assessment of the state of the ocean pollution and its

impact on marine ecosystems, and an improved international system allowing

the monitoring of the factors necessary for the understanding and forecasting

of disasters and implementation of an efficient warning system."

The EARTHWATCH speaks to a broad spectrum of environmental phenomena,

certainly one of which is pollution from petroleum and petroleum products.

The IGOSS Committee in its considerations and reports has recognized the value

of the results from the Pilot Project as an input to UNEP and, in turn, UNEP

has recognized the value, and I may stand corrected, but I believe is providing

a modest level of support.

In the last 3 days, experts from all over the world have gathered here

in this building to review the state-of-the-art in preparation for the workshop.

68
Now, what is the objective of the Pilot Project? Let me refresh your

memory (although it probably is unnecessary) —to initiate and evolve an internationally coordinated program for marine pollution monitoring, initially in

selected ocean areas. To a degree, the terms of reference indicate that the

Workshop will be developing the details to provide an exchange of data and

information among nations (probably very significant) and intercomparability

of data for making assessments of the periodic state and degree of contamination of the marine environment. There must be a degree of standardization

if we are going to compare the results obtained from the Pilot Project, as these results are from different ocean areas of the world.

The highlights of the review for the last 3 days spoke to sampling and

analytical methods, standards and inter comparison criteria, oil in marine

organisms and sediments, analytical techniques for each, as well as tar balls,

particulates, and aromatic hydrocarbons.

Now what specifically is the workshop charged to do? With the results

of the Symposium in mind, with the objectives of the Pilot Project always in

front of them the workshop is charged to:

- Review and finalize the operational plan. Review and finalize means

in part: review, assess, modify if needed, and finalize.

- Recommend studies and actions required for expansion and development

of the Pilot Project. The Pilot Project, just as the term "pilot"

implies, is the initial step in what IGOSS, IOC, and others involved,

hope will become an on-going operational global concept.

- Define the recommended technical assistance programs and training and

education projects. These to highlight the needs so that the scientists,

particularly those in the developing countries, may receive the training needed so that they may become an integral part of the Pilot Project, and even more important, of the continuing nature of the monitoring program on down the road.

- Focus the R&D aspects, if you will, the technical aspects, to speak to

the methodology, analytical standards, data handling, contents of the

final report, what guides and manuals will be needed for those participating in the Pilot Project, recommendations as to whom should have

the responsibility for the preparation of these guides, and in what

manner the technical assistance programs will become involved.

Now, I spoke to the elephant, the trunk, and the worm. I was just going

to say, let me turn to the worm, but I simply refuse to put the data management aspects of this in the category of a can of worms.

If I could have the next slide please. I am very interested in showing

you a concept we have been working on, are developing somewhat as a national

concept, and hope to broaden to an international concept of how environmental

data should be managed. What this speaks to is that data management should

start when the concept is developed. I am using it here at this time primarily

because the project with which you have been concerned during the last 3 days

69
and which the Workshop will continue to be concerned with seems to very neatly

highlight this concept. Considerations concerning the handling of the data

continue through the planning phases, which will really be the Workshop, on through the operational aspects. In other words, plans should be made for

the manner in which the data that will be recorded on board the ships and in

the labs will be handled. These data are being collected for a purpose.

Therefore, every effort should be made to see that the data in their reasonably

standardized forms ^as quickly as possible are in the hands of the users, the

primary users. Then they should be made available to the centers, whether

they happen to be the national centers, or the World Data Centers, or to a group such as ICES, the International Council for the Exploration of the Sea,

so that these data may then have a wide dissemination to the secondary users. Whether the secondary users happen to be scientists, nations, or whoever may

be interested.

So Mr. Chairman, I think the proper thing at this moment is to wish those

that will be in the Workshop, Godspeed, and to extend the sincere appreciation

of those involved to the participants during the last 3 days and particularly

to all of you who have had the intestinal fortitude to sit here until this

late hour without having a coffee break. Thank you very much.

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of

a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974

(Issued December 1974)

.

70
CONTRIBUTED PAPERS

71

TOPICAL SESSION I.

Sampling Methods and Techniques; Oil Slicks,

Tar Balls, and Particulates

73

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposltim and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

QUANTITATIVE MONITORING AND VARIABILIIT OF PELAGIC TAR IN THE NORTH ATLANTIC

James N. Butler

Division of Engineering and Applied Physics

Harvard University

Cambridge, MA 02138

Byron F. Morris

Bermuda Biological Station for Research

St. George's West, Bermuda

Chiantitative collection of pelagic tar (petroleum residues found on the surface of the open ocean) began in 1969 [1,2] and has been

carried out in many parts of the world since then

[3,4]; but few data are available to estimate the sampling error. The question which we address

in this paper is: If a single sample is taken at

a particular place at a particular time, how

representative is this amount of tar of the amounts which would be collected by repeated sampling?

There are three types of data which can be

used to answer this question. The first and most

abundant type is the series of values obtained

along a single cruise track. In most such published data stations (where neuston tows are of the order of 1 km in length) are usually hundreds

of kilometers apart; and so from such a set, of data one cannot tell whether the large variations

observed reflect variations in the amount of tar on a scale of tens to hundreds of meters (e.g.

Langmuir [5] windrows) or tens to hundreds of kilometers. The most closely spaced stations

[6] show data with variability of a factor of 50 on a distance scale of 1 km. Needless to say,

a single cruise track can tell nothing about time

variation unless the track is repeated at a later

date.

Thus the time series data we have obtained at Station S [7] (32°10'N, 64°30'W) near Bermuda,

although meager, are uniquely valuable in assessing the variability of sampling by other investigators. This time series, taken biweekly since

1971, was augmented by a series of tows at approximately two-hour intervals in February and August

1972. The short-term series were intended to give information about the reliability of the samples in the long-term series. Full tables and details of method are given elsewhere [3].

Since variations occurred of more than a factor of 100 in the amount of tar collected,

and variations of ever a factor of 10^ in the amount of Sargassum collected in the long time

series, it seemed plausible to inquire whether

the tar was in some way associated with Sargassum

colonies, since such colonies collected by dip

net often contain tar lumps. Figure 1 shows the correlation on a log-log plot. Although there

is a slight correlation (R = 0.39) in that

extremely high values for Sargassum do not occur

together with extremely low values for tar, or vice versa, it would appear that substantial quantities of tar can occur without the presence of any Sargassum (as of course is observed in waters

other than the Sargasso Sea), and that quite large

ratios (250) of Sargassum to tar can also be observed. The ratio of arithmetic mean wet weights

is 25 Sargassum to 1 tar (the ratio of geometric

means is of the order of 10 to 1), corresponding

to a line of slope unity drawn through the cluster

of points.

The raw data of the two short-term time

series are displayed in Figure 2. Note that even

at intervals as short as an hour or two, variations in the amount of Sargassum and tar of a fac- tor of ten or more are quite frequent, in spite

of a deliberate attempt to average out any inhomo- geneous distribution due to the Langmuir [5] circulation. For example, tows typically were made

in a circle of approximately 1 km diameter.

Depending on wind conditions, Langmuir windrows

are spaced from 10 to 50 meters apart , and such

a tow would have intersected 20 to 100 windrows

at varying angles.

Correlation of Sargassum and Tar in these series (Fig. 3) followed the same pattern as the long time series, except that in February (S-356) the Sargassum/ tar ratio was of the order of 150, and in the August series (S-365), this ratio was

only about 2. Correlation was not significant;

R=-.03 and +0.14 respectively.

As is clear from Figures 1 and 3 , and as we have noted elsewhere [3,8], these values are more

or less normally distributed on a logarithmic

scale, and thus the geometric mean and the relative standard deviation (ratio to the geometric

m6an) are the relevant statistical parameters for describing a set of data. These parameters are displayed in Figure 4. Note first that the relative standard deviations of the tar values for S-356 and S-3b5 are essentially the same, although

the average values differ by a factor of 10. On

the other hand, the relative standard deviation

of Sargassum in August (S-365) was much larger

than in February (S-356). Furthermore, the standard deviation of the two short-term time series

is only slightly smaller than for the two-year

series of biweekly measurements. This implies

that the additional variance resultinf; from longterm cycles is relatively small compared to the variance of sampling.

To investigate the long-term and short-term

cyclic behavior of the tar and Sargassum data,

a power spectral analysis of the time series was made [9,10]. Although the number of data points

was really insufficient for any details of cyclic

behavior to be elucidated, certain aspects of the time series were readily apparent from the results. Figure 5 shows the power of spectral estimates

for Sargassum and tar each taken independently,

and also the cross-spectrum amplitude. The annual

cycle of Sargassum [11] shows up clearly as does

a seven-v;eek cycle. In the tar spectrum, the prominent feature is a cycle of approximately ten weeks duration. The cross-spectrum essentially

follows the Sargassum but with less pronounced

75
features. The occurrence of approximately two- month cycles for both Sargassum and tar lends some credence to the notion that this reflects mesoscale processes of ocean circulation with a relax- ation time of approximately two months [12].

Spectral analysis of the short-term series

shows no significant structure (Fig. 6) and the dependence of spectral estimates on frequency is characteristic of a Markov-like process with cor- relation becoming weaker as the time separation

between stations becomes greater. For the best analysis of time series, data should be obtained

at regular intervals without any omissions. No data presently available on pelagic tar satisfies

this criterion rigorously, including our own.

In suDinary, the variability of sampling by neuston net for either pelagic tar or Sargassum

Is very high, and even the results of successive

tows may differ by a factor of ten. The standard deviation is of the order of 0.5 log units, a factor of 3. The standard deviation of the geometric mean of ten to fifteen neuston tows may be estimated to be approximately 0.13 log units, or 40%.

In other words, a single neuston tow is representative of the general area where the tow is made

only within a factor of ten . In view of this,

elaborate techniques for flow measurements [3] are unwarranted, and correction to dry weight or removal of non-petroleum materials, worthwhile

only if the relative amount of these materials in the tar lumps is considered to be of intrinsic

interest. The lOC-WMO recommendations [13] for analysis to determine dry weight thus involve

a great deal of unnecessary labor and should be replaced by determination of a simple wet weight

value .

Acknowledgements

This work was supported by the U.S. National

Science Foundation, International Decade of Ocean

Exploration (Grant GX32883), the U.S. Office of Naval Research (Contract ONR 10/241.24), and the Bermuda Government. The authors thank Mr. George

Taggett and Mr. Harry Fox, skippers of the Panulirus II, Miss Jill Cadwallader for laboratory

assistance, and Mr. Ivan James for computer work.

References:

[1] Horn, M. H. , Teal, J. M. , Backus, R. H.

,

Science 168, 245-6 (1970).

[2] Morris, B. F. , Science 173 , 430-2 (1971).

[3] Butler, J. N., Morris, B. F. , Sass, J., Pelagic Tar from Bermuda and the Sargasso

Sea , Bermuda Biological Station, St. George's

West, Bermuda, Special Publication No. 10

(1973) . [4] National Academy of Sciences, Petroleum in the Marine Environment , Washington, D.C.

(1974) . [5] Langmuir, I., Science 87, 119-123 (1938).

[6] Polekarpov, G. G., Yegorov, V. N. , Ivanov,

V. N., Tokareva, A. V., Feleppov, I. A., Priroda, No. 11 (1971). Translation for Pollution Abstracts No. 72-5TC-0451. Data reproduced in Ref. 3. [7] Morris, B. F. , and Schroeder, E. , Hydro- graphic Observations in the Sargasso Sea off

Bermuda: May 1967-February 1973 . Bermuda

Biological Station, St. George's West, Ber- muda, Special Publication No. 12 (1973).

[8] Morris, E. F. , and Butler, J. N., Proc. Joint

Conf. Prevention and Control of Oil Spills , American Petroleum Institute, 521-9 (1973).

[9] Fishman, G. S., Spectral Methods in Econo- metrics , Harvard University Press (1969).

[10] Dixon', W. J., Ed., Biomedical Computer Programs , University of California, Los Angeles,

(1970). Program BMD02T.

[11] Deacon, G. E. R. , Geographical J . 99, 16-28

(1942).

[12] Robinson, A. R. , Private communication.

[13] IOC-WMO/IPLAN-II/3, Annex V, item 6.

Key Words: Petroleum, Tar, Sargassum, Sargasso

Sea, North Atlantic, Neuston, Sampling, Analysis

of tar.

This is Contribution No. 598 from the Bermuda Biological Station.

1 1

1 I I I 1 I

I

1 1 1—I Mill 1 1 1 I I M I STATION S-341 TO "^3"

Figure 1. Correlation of wet weight of Sargassum

and pelagic tar. The line corresponds

to a 25:1 ratio.

76
1000c—

r

8-9 AUG 72 S-365

-~ 100-

s3

(O

CO<

oc. <w

oco

a:

0.1 NOON 2PH 4

S-356 TAR: 15-16 FEB 72

1.0 10 WET WEIGHT OF TAR,mg/m2

i

100

Figure 3.

MIDNIGHT 4AM 6 8 10 NOON

Figiire 2. Short-term time series of Sargassum

and tar obtained in February and August 1972, stations S-356 and S-365.

Correlation of Sargassum and tar: Data

of Figure 3. Bars at top give statistics for tar, at the side give statistics for Sargassum . Central line is geometric mean, white bar is relative

standard deviation of mean, dark bar

is relative standard deviation of single datum, and extreme limits give

the range.

Figure U, Comparison of short-term statistics (left) with long-term statistics (right), Bars express same data as Figure 3.

77
o

WEEKS/ CYCLE

50 20 15 )0 8 6 4

0 0.1 0.2 CYCLES/ WEEK

Figure 5- Spectral analysis of long-term time

series

.

+ or X O

CYCLES/ hr CYCLE/ hr

Figure 6. Spectral analysis of two short-term time series.

78
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), FxoceedlDgs of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

TAR BALL LOADINGS ON GOLDEN

BEACH, FLORIDA

LTJG W. A. Saner

CAPT M. Curtis

U. S. Coast Guard

Research and Development Center

Groton, Connecticut 06340

Disclaimer

The contents of this report represent

the findings and views of the author who

is responsible for the facts and accuracy

of the data presented. The paper does

not necessarily reflect the official views

or policy of the U. S. Coast Guard.

The sampling of beach tar from a sandy coast was performed for one year

in order to evaluate the effect of sampling zones of varying sizes and the effect

of tar build-up on the beach with time.

In addition, the effect of wind on tar

deposition was also determined.

The area selected for study is

located within a uniform twelve mile

tract of beach running nearly due north

and south between Fort Lauderdale and

Miami. The actual sampling site is

located along a l.M- mile stretch belonging to the town of Golden Beach. This area is reserved for use only by local

residents, and is uninterrupted by bays,

cuts , or breakwaters

.

The area was divided into five zones : 20, 40, 80, 120, and 160 feet in width,

with interzone spacings of 60, 120, 240,

300 feet, respectively. The zones ran consecutively from the smallest (20 ft.) zone situated furthest north to the

largest (160 ft.) zone situated furthest

south. The zones were staked out andcleared of all debris prior to sampling.

Usually all five zones were sampled

each weekday (five days per week) over

the entire period (September 1971 to

September 1972). However, due to sporadic

mechanical beach cleaning by bulldozer

and occasional severe weather conditions

some weekend sampling was performed in

order to compensate for lost weekday

coverage

.

The actual tar pick-up involved non- replacement sampling and weighing of all

solid and semi-solid pieces of tar/oil.

Frequent surprise spot checks by an independent sampler rarely turned up more

than ten percent additional tar/oil. All

sampling was accomplished within 3-1/2

hours of low tide since almost all of the

tar stranded at the high tide mark in a narrow zone 4-5 feet in width.

The presence of non-petroleum

inclusions in the tar samples (shell,

sand, water) inflated the weight of

stranded tar so that the actual petroleum

weight represents approximately 7 5 percent

of the reported weights.

No extraneous fluctuations are evident in tar loading on the smallest

(20 ft.) zone when compared to the

largest (160 ft.) zone. Figure 1 presents

total monthly weights of tar stranding

in the 20, 40, and 160 foot zones. All

data was normalized to 100 foot zones. Although the same general fluctuations

are consistent for these zones, proportionately more tar is deposited in the

smallest zones. However, this is not

due to relative size differences between

zones, but rather due to their relative

positions on the beach within the tract

area. Relative monthly fluctuations in

tar loadings in each zone were compared

using root-square differences. This was

done after normalizing monthly totals

from all zones to the total annual tar

loading value in the 20 foot zone. Essentially this allowed comparisons of

relative monthly fluctuations rather

than absolute amounts. In this way the

beach bias shown in Figure 1 was negated.

The root-mean square values are presented in Table 1 as percentages of

the total annual 20 foot zone tar value.

20 FT ZONE

40 FT ZONE

160 FT ZONE

9 10 11 12 1 1 2 3 4 5 6 7

Figure lo Total monthly weights (gm) of

oil from the 20, 40, and l60

feet zones (normalized to 100

feet zones).

79
Table I. Root Mean Squares Expressed

As Percentages Of The Total

Annual Oil Loading In The

2 0 Foot Zone.

40 80 120 160

20 9.75 11 .27 9.98 9.25

HO 4 .65 7 .10 6.57

80 8 .42 7 .04 120 8. 67

The maximum observed difference is 11.27

percent. It is interesting to note that

this did not occur between the smallest

and largest zones , but rather between

the 20 foot zone and the 80 foot zone. These data indicate that a zone as small

as 20 feet in length along the beach

produced tar accumulation data that was

as reliable as a zone eight times as large (160 ft.)

A beach bias is demonstrated in

Table 2 ; proportionately more tar was deposited on the northernmost zones than

on the southernmost zones. The reason

why more tar should be deposited in one area than in another is not clear until

one examines possible climatological

influences on tar deposition.

Table II. Zone (Ft.)

20 40 80 Total annual

oil loading 15,517 24,133 34,101

(gm)

120 160

42,284 66,384

Figure 2 demonstrates the effect

of wind direction on tar deposition. All

net wind vectors were calculated by

averaging wind direction every three

hours over the previous 24-hour periods

prior to sampling. Forty-five degree

sectors were used; that is, all previous

net wind movement vectors between 22.5°

and 67.5° were graphed as 45° for each

major wind direction plotted. Only those

sampling days directly preceded by a sampling day were included in order to negate any build-up effect of tar on the

beach

The ratios are as expected when the

wind was from the south (180°); however,

the ratios were distorted when the wind

came from either east or west. Essen11* »CTU»t / 'A ~ / «»Tio ( to m / ' ^ >1

1^ EXPECTED ( 40 >T ) RATIO -2 (20 FT) ^ A EXPECTED ( SO PT > ^ RATIO -4 (20 FTV

5 ^ArniAL ( BO FT ) ^RATIO (20 FT) \ \

\ \

Figure 2. Oil loadings (gm) in the 40,

80, 120, and 160 feet zones ratloed to oil loading (gm)

in the 20 feet zone versus

net wind direction of 24 hour

periods prior to sampling.

tially this means that east or west winds

result in more tar being deposited in

the northern end of the sampling tract,

than in the southern end. Strong correlation between heavy oil deposition and

northeast winds (000° to 090°) is shown

in Figure 3

y L \

Figure 3. Total oil loadings (gm) from

all survey zones versus net

wind direction of 24 hour

periods prior to sampling.

80
The expression,

A(t) = ^(1 -e"^"^)

defines the amount of tar present on the

beach at any time, where r = rate of tar

being stranded, k = constant, t = time in

days. Two assumptions were made:

a. The rate at which tar washes

ashore is constant.

b. The rate at which tar is

removed from the shore is proportional

to the amount present on the beach.

Substituting the average of all one- day tar accumulations (7 37 gms ; n = 156)

and the average of all three-day tar

accumulations (IQi+O gms; n = 35) into the

above equation gives r = 1246 gms/100

linear feet of beach/day, k = 1.162. These

values produce a beach time constant (that

is, the time necessary for the beach to

reach one half the load of tar it will

ultimately carry at t = <») of . 597 days

or 14.3 hours, and r/k - 1073 as the

assymptotic value: as t approaches »

,

A(t) approaches 1073. In three days this

coastal area reaches 9 7 percent of the

maximum amount of tar pollution (by

weight) that it will support at infinite

time (having started with an initially

tar-free b.each) . The average of all twoday tar accumulations (n=21) produced a value of 759 grams/lOQ linear feet of

beach, whereas the predicted value from

the above equation was 9 68 grams/ 10 0 linear feer of beach. This leads one to believe that n = 21 samplings is too small

to be reliable. However, since all 3, 4,

and 5 day sampling intervals represented

the same near-equilibrium, tar-loading

condition, the average of all such

samplings (n= 43) produced a value of 1070

grams/100 linear feet of beach. This is

in very close agreem.ent with the value of

107 3 grams predicted above utilizing 156

one-day accumulations and 3 5 three-day

accumulations. Therefore, as few as 35 samplings are sufficient to produce an accurate average tar loading value.

Key Words: Equilibrium, value, beach time

constant , beach bias

.

81
N
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

TAR BALL SAMPLING IN THE WESTERN

NORTH ATLANTIC

William E. McGowan

William A. Saner

Gary L. Hufford

U. S. Coast Guard

Research and Development Center

Groton, Connecticut 063U0

Disclaimer: The contents of this report represent

the findings and views of the authors who are re- sponsible for the facts and accuracy of the data

presented. The paper does not necessarily reflect the official views or policy of the U. S. Coast

Guard.

The U. S. Coast Guard conducted a sampling program in the western North

Atlantic Ocean beginning in 1971 to determine the quantity and source of

floating tar "balls" in the marine

environment. Most of the sampling was performed from Coast Guard weather ships

deployed at four ocean station sites : Bravo (56° 30' N, 51° 00 'W), Charlie

(52° 45' N, 35° 30' W) , Delta (44° 00' N, 41° 00' W) and Echo (35° 00' N, 48°

00' W) (Figure 1). The series sampling

at each location allowed a determination

of variability and estimation of the

average amount of tar present.

The method used to obtain tar ball

samples utilized a neuston net (000

mesh) attached to a fiberglass frame

which was towed from the side of the

ship. The frame (1.00 x 0.35 m) has a built-in flotation chamber to keep half

of the open end of the net above the

surface of the water. A mechanical

propeller-driven flowmeter was mounted

to the lower part of the frame just

inside the mouth of the net. The net

assembly was attached to an adjustable

towing bridle so that the assembly

could be adjusted to ride smoothly. The

assembly was then rigged to a twenty

foot boom located near the bow of the

ship. This forward mounting of the boom

allowed for sampling from essentially

undisturbed surface water.

Tpwing speeds ranged from drifting

to 3'. 5 knots (1.8 m/sec) with the

duration of tow being 45 to 60 minutes

dependent on wind conditions . Most of

the tows were made during daylight

hours. The majority of the tows were

made into the winds, although 31% were

made perpendicular to wind direction.

The sampling system was effective in sea

states up to force 6. All tar balls collected during each

tow were individually counted whenever

possible and then combined into a single

sample. These samples were stored in

glass jars having teflon-lined lids and were refrigerated at low temperatures

whenever possible. Petroleum smears on the net were noted , but were not included

in the determination of tar ball concen- trations . Daily logs were maintained for all

tows noting: position, date, time, speed

of vessel, duration of tow, meteorological

data, sea state, and specific observations

with respect to sampling and collected

samples

.

. Tar ball concentrations were determined at a shore-based laboratory and

expressed as wet weight of tar (mg) per

unit surface area sampled (m2). In addition the percentage of water contained in all tar balls collected was determined by azeotropic distillation with

benzene, and was found to range from

virtually none to as much as 51% by

weight, with the average being 21%.

A major feature of the data was the

extreme variability in tar ball concen- trations at all ocean stations except

Bravo. The standard deviation in tar

ball concentrations was usually of the

same magnitude as the sample mean for

any series of tows. As an example, a series of 8 tows were made at Echo during

a 48 hour period. The tar ball concen- trations varied by a factor of 12 in

this series of tows. Altering sampling

procedures such as tow speed, direction

and time of tow, did not decrease this

large variability. It appears that the

observed variability is due to environmental parameters . A greater knowledge

of winds, currents, and waves in the

sampling area might explain this sampling variability. A total of 214 neuston

tows have been conducted at these four ocean stations. Although the variation

in sampling is quite large, certain

trends are evident. The concentration

of tar balls increases from virtually

zero at Bravo to greater than 2.6 mg/m^

at Echo (Table I). This north to south

trend was noted in all three years of

sampling. The variation is too large

to determine if an increase in tar ball

concentrations has occurred at any

given ocean station since 1971.

The higher concentrations of tar

balls found at Echo is not entirely unexpected. The ocean station is located

in the Sargasso Sea. This Sea is bordered by a subtropic anticyclonic gyre . This

rotation of the gyre moves surface water

toward the center creating a "catch all"

83
basin for floating materials. Assuming concentration of tar balls in the Sar- that the residence time of tar balls on gasso Sea.

the ocean surface is reasonably long

then one would expect to find a higher Key Words: Neuston net, open ocean,

tar balls.

Table I. Summary of Tar Ball Concentrations at Four Ocean Stations in Western North

Atlantic Ocean (1971 - 1973).

Ocean Station Range of Concentration Ocean Station Mean Concentration

(mg/m2

)

(mg/m2

)

Bravo 0 - 0.00 3 Bravo ' 0.00 0 Charlie 0 - 1.83 Charlie o.l2

Delta 0 - 10.73 Delta 1.15

Echo 0 - 21.62 Echo 2.64

Figure 1. Location of the four ocean stations in the Western North Atlantic.

84
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

EVALUATION OF THIN FILM OIL SAMPLERS

LTJG W. J. Chang

U. S. Coast Guard Headquarters CG-DET-1/62)

Washington, D. C. 20590

J. R. Jadamec

U. S. Coast Guard Research and Development Center Avery Point

Groton, Connecticut 06340

Introduction and Objective

Portions of the 1972 Federal Water

Pollution Control Act require that the Coast Guard maintain a system for the detection of discharges of oil and other hazardous polluting substances, disseminate

information on these discharges, document

violations of the act and determine if removal of the oil or hazardous sub- stance is properly done. In order to fulfill its responsibilities, the Coast Guard is developing sampling

systems. One of the work units in the sampling systems project is the development of a boat deployable thin film oil

sampler. This paper deals with the evaluation of four prototypes which were

designed for collecting oil samples from

thin films for identification purposes.

It is felt that the results and conclusions contained in this paper will be directly applicable to the Marine Pollution

Monitoring Pilot Project.

The objective of the teats was to evaluate the samplers':

1. Handling characteristics under practical conditions.

2. Maintenance and repair requirements.

3. Efficiency of oil pickup.

4. Ability to maintain the chemical

integrity of the oil.

All of the samplers tested utilized an oleophilic sorbent while two of those

tested used a surfactant as well. Figure 1 shows the four samplers which were tested. From the top, clockwise, are Shell Pipeline,

Marconsult, Poseidon nets, and Coast Guard R&D.

Figure 1. Collective presentation of samplers.

Description of Samplers

Figure 2 shows the Poseidon Oil Net which is a double layered polypropylene

yarn sleeve held open at the mouth by a steel hoop and knotted at the tail. The

net is bridled at the mouth and is towed through an oil slick in order to collect

a sample. The polypropylene yarn serves

as both the oil sorbent and the supporting

net material. After a sample is collected,

the sampler is simply dropped into a can for shipment to an analysis lab. This

sampler is expendable and therefore no cleaning is necessary.

Figure 2. Poseidon oil net.

85
Figure 3 shovs the Marconsult sampler

which Is a modified stainless steel sieve

with top and bottom covers, housing a polyurethane foam pad. The sieve is supported by a chain harness clipped

onto the sampler's outer edge. After venting the top cover and removing the bottom cover, the sampler is dipped into

the slick in order to collect a sample. After a sample has been taken the bottom

cover is replaced and the top cover sealed

so that the sampler may be shipped to a lab

for analysis.

Figure 3. Marconsult sampler.

The fourth sampler (Fig. 5) was developed by the Coast Guard's Research and Development Center in Groton, Connecticut. The donut shaped

sampler uses a polyurethane wad on a central strut and a surfactant along

its inside edge. The sampler is placed

in a slick and the surfactant acts to push the contained oil into the center where it is collected by the foam. After the oil has been collected the sampler is removed from the water and

the polyurethane placed in a sample

jar for subsequent analysis.

Figure 5. Coast Guard R&D Center sampler.

The Shell Pipeline sampler (Fig. A) is constructed of corrugated aluminum.

Polyurethane foam provides flotation. After saturating the central polyurethane

wick with a surfactant, the sampler is lowered into the slick. The surfactant

pushes the oil contained by the sampler

towards the inside periphery where it is collected by polyurethane strips. After

sampling has been completed, the strips are

removed and placed into a sample jar for subsequent analysis.

Figure 4. Shell pipeline sampler.

Sea Tests

Sea tests were conducted in order to evaluate the samplers':

1) Handling characteristics under practical conditions.

2) Maintenance and repair requirements.

The oil used during the sea tests was

soybean oil. Results of the tests indicated that one of the samplers was

superior to the others as far as ease

of deployment and maintenance requirements were concerned . This however

,

was not the only factor Involved in the evaluation since tank tests were also

conducted.

Tank Tests

The objective of the tank tests was

to evaluate:

1) The efficiency of oil pickup of the samplers.

2) The ability of the samplers to maintain the chemical integrity of the

oil.

86
The samplers were tested by deploying

them in slicks with nominal thicknesses

of 10"^ 10"^ and 10"^ cm. Test oils used during tank tests were a No. 2 Fuel Oil, a Bunker C, and a South

Louisiana Crude. The samples collected

during these tests were analyzed

color imetrically to determine the efficiency of oil pickup and by gas chromatography, fluorescence

spectrophotometry, and infrared

spectrophotometry to determine the

ssunplers' ability to maintain the chemical integrity of the oil.

Tank Test Results

The following conclusions were

reached after analysis of the tank test results:

1) All of the oil absorbent materials

tested contained extractable chemical

compounds.

2) Both fluorescence spectrophotometry

and gas chromatography appear capable of oil identification through comparison of "fingerprints" of oil samples to "fingerprints" of the original oils.

3) Infrared spectrophotometry is only

capable of oil classification under these tests conditions.

4) For the express purpose of characterization of the source of an oil

sample (identification), the use of a solvent to extract the absorbed oil should

be avoided. If the quantity of absorbed

oil permits mechanical removal, then this technique should be used since chemical

characterizations are enhanced.

5) The surfactant used did not interfere

with the identification of the test oils.

Determination of Overall Ranking

The results of the sea tests and the tank tests were assembled and the samplers were ranked in the following categories:

infrared, gas chromatography, volume of oil collected, efficiency of oil collection,

sea tests, fluorescence, and sampling time.

It was felt that neither fluorescence nor sampling time discriminated between

samplers to a sufficient degree to justify

rankings. Therefore, all samplers were

assigned equal scores in these categories.

The overall ranking of the samplers

(Table I) indicates that the Coast Guard

R&D sampler was best, but it is recognized that there is room for improvement. It is further recognized

that the substitution of one sampler's

foam for another's would probably result

in some change in the finishing place for those samplers

.

TABLE I OVERALL RANKING OF SAMPLERS

SAMPLER RANK INFRARED GAS VOLUME EFFICIENCY SEA TESTS FLUORESCENCE SAMPLING AVERAGE

CHROMAT- OF OF OIL TIME SCORE TOGRAPHY COLLECTED COLLECTION

OIL

R&D 1st 1

MARCONSULT 2nd 2

SHELL 3rd 3

POSEIDON 4th 4

2.5

2.5

2.5

2.5

2.5 2.29

2.5 2.43

2.5 2.43

2.5 2.86

Conclusions and Recommendations

In designing a technique for oil

sampling, consideration must be given to the techniques by which the sample will be

analyzed. The sorbents used in all of these samplers contained extrac tables which interfered with analysis. The matter

was further complicated by a variation in extractables from manufacturer to manufacturer as well as from lot to lot.

Although Improved quality control or pretreatment of suspected source samples

might alleviate the problem, elmination

of the source of the contaminants is recommended.

The Coast Guard's present efforts are directed towards the substitution of glass

wool for the sorbent and the elimination of solvent extraction. The following

recommendations are specifically addressed

87
to the development of an oil sampling

technique for the Marine Pollution Monitoring Pilot Project:

1) Sorbents such as polypropylene and polyurethane should be avoided

.

2) If sorbents are used (due to their

high oil collection efficiency) infrared

spectrophotometry can not be used for identification of the samples. Gas chromatography and fluorescence

spectrophotometry appear capable of identification under these conditions.

3) Solvent extraction should be avoided;

if the quantity of oil absorbed is sufficient,

mechanical removal is preferable.

4) Glass wool may be used as a collecting

medium. If glass cloth is used it must be

of the untreated variety as the treated variety contains potential contaminants.

References

(1) Allen, Alan A. and Fausak, Leland E.

,

"Development of an Oil Slick Samplltig

Device Suitable for Use from a Helicopter or Surface Vessel", Final

Report Project 7 24242.3/3 USCG

CAug. 1972).

(2) Cochran, R. A., "The Design and Con- struction of an Oil Slick Sampling

Device", Final Report Project 734242.3/1

USCG (Sept. 1972).

(3) Hirshman, J. and Maiman, J, D. , "Design and Construction of an Oil

Sampling Device", Letter Progress

Report Project 734242.3/2 USCG

(Nov. 1972).

(4) Schatzberg, Paul, "Investigation of Sorbents for Removing Oil Slicks from Waters", Final Report Project

724110.1/2/1 USCG (Nov. 1971).

(5) Schatzberg, Paul and Jackson, Drew F., "Remote Sampler for Determining

Residual Oil Contents at Surface

Waters", Final Report Project 734209.9

USCG (Nov. 1972).

Key Words: Oil sampling, Sorbents,

Surfactants, Oil identification.

Appendix A - Infrared Spectrophotometry

Infrared studies were performed using

a Perkin-Elmer 567 Spectrophotometer in conjunction with a Wilks FMIR beam condensing attachment. The KRS-5 crystal was

dipped repeatedly into cyclohexane

solutions of the absorbed oils. Blank

cyclohexane extracts of the sorbents were

also run. The residues coating the plate

after evaporation were analyzed.

Interpretation of the infrared traces was made primarily by examination of the "fingerprint" region from ca. 1300 - 600 cm-1, with particular attention to the 880 - 700 cm-1 region.

Appendix B - Ultraviolet Fluorescence

A Perkin - Elmer MPF-3 Fluorescence

spectrophotometer was used. Spectra were

run on the cyclohexane/oil solutions

eluted from the absorbents. Blank

cyclohexane extracts of the sorbents were

also run. The emmission spectra from

260 - 500 nm were obtained with 254 nm

excitation.

Appendix C- Gas Chromatography

A Varian Gas Chromatograph Model 2800 was used. Chromatographs were programmed

from 75° C to 275° C (? 6°/min. The column

was 5 X 1/8" S. S. packed with 3% SE-30 on Variport (100/120) mesh. 10 yul of the oil in cyclohexane mixture was Injected.

The carrier gas was helium. Blank

cyclohexane extracts of the sorbents and pure cyclohexane were also run.

88
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

OIL SPILLAGE MONITORING,

SAMPLING AND KECOVERY SYSTEMS

J. G. ZAHKA

Durham Associates, Inc. 100 Elm Street

Milford, N.H. 03055 U.S.A.

Products have been developed by

Durham Associates, Inc. for use in con- trolling marine pollution from petroleum.

They incorporate a unique selectively

transmissive membrane which, while preventing the penetration of water, allows

oil to flow through easily. Modifications

of this membrane have been used in the

construction of oil spill detection systems, oil recovery devices, and surface

oil samplers.

The purpose of this symposium is to

discuss and plan a program to evaluate

marine petroleum pollution. It will be a comprehensive program monitoring several

forms of oil pollutants over large areas

of water. Pollution baselines will be determined. The most important information

which should be gained from the survey is

to ascertain the sources of the marine oil

pollution. Without determining and con- trolling the entrance points of the oil

into the environment, the environmentally

conscious community can only look with

despair at the climbing oil pollution

baselines. Once the potential sources have been determined, they should be mo- nitored continually to reduce the damage

to the environment. With the proper mo- nitoring procedures, a potential 10,000

gallon oil spill can be prevented before

only one gallon has reached the water.

Economically, those involved in the cleanup of oil pollution find that the cost of

removing equal volumes of oil from water

increases almost exponentially with the

residence time of the oil in water. The

relative ease of removing 500 gallons of

oil just as it enters the plant effluent

stream can' be appreciated when compared

to trying to remove the same 500 gallons

once it has dispersed in the harbor.

The basic technology of the oil spillage monitoring, sampling and recovery

systems developed by Durham Associates,

Inc., centers on the hydrophobic, lypo- philic properties of certain materials.

Surface properties of a porous substrate

are adjusted so that the water does not

wet the surface of the pores. In equilibrium, the propensity of a liquid to

wet a solid surface is determined by the following equation:

^LV COS e = - y^^

where y is the surface free energy, LV is

the liquid-vapor interface, SV is the solid

vapor interface, SL is the solid- liquid

interface and 9 is the contact angle of

the liquid with the solid surface. By mo- difying Ygy and Yg^^ , the angle e can be

affected for a given liquid. It is desired that water not wet the membrane so

9 is made greater than 90° for water.

The standard capillary rise equation

for a cylindrical capillary is:

AP = (2y cos 9) / r where AP is the pressure difference across

the liquid-vapor meniscus ; Y is the liquid

vapor surface tension; r is the radius of

the capillary and 6 is the contact angle

of the liquid with the solid. If 9 is

greater than 90°, then COS 9 is negative,

causing AP to also be negative. In this

case the liquid is retarded from entering

the capillary by the negative pressure.

This phenomenon is called capillary depression and is the means by which the

membrane in the devices herein discussed

retards the penetration of water.

Oil, on the other hand, has a contact

angle of less than 90° with the pore surface. The pressure across the oil-vapor

meniscus is positive, causing the oil to

flow into the pores. Once into the mem- brane pores, the oil will continue to flow

through the membrane. In this manner the

membrane will continuously separate oil

from water by allowing the oil to pass

through the porous substrate but retarding the passage of water.

The oil spillage detection system incorporates this unique membrane to con- stantly monitor the water's surface for

oil slicks. The membrane is floated at the air-water interface so that any oil on the surface will contact the membrane.

Once at the membrane surface, the oil

enters the pores and flows through. The

oil which has passed through the membrane

collects in a small receptacle where the

presence of the oil is detected by a float

activated switch. The float switch is a simple device and the single moving part

in the system. A float, shaped to the

contour of the receptacle normally rests

on the receptacle floor. As oil flows in,

the float lifts, moving an integral permanent magnet in relation to a hermetically sealed SPDT magnetic reed switch. When

the preset alarm threshold oil quantity

has been accumulated, the switch is actuated, transmitting a real-time alert and

initiating a desired chain of events. The

detector communicates the presence of oil

to a monitor by wire or by VHP radio

transmission

The oil spillage detection system re- quires no electrical power or human effort

until an oil spill has been detected. It

89
constantly monitors the water's siirface

independent of lighting and weather con- ditions. A small sample of oil is collected so that it may be analyzed to determine the source of the pollution.

The same basic technology is used to

make effective clean-up devices. While

the liquid collected by many present oil

spill collection devices contains a large

percentage of water, a recovery device incorporating this selectively transmissive

membrane collects oil which is virtually

free of water.

One such configxiration suitable for

bilges and ballast tanks contains a mem- brane in a fluted cylindrical configuration. The containment receptacle again

contains a float switch, but in addition

to transmitting information as to the

volume of oil being separated, it activates a pump which transfers the oil from

the containment receptacle to a larger

holding tank. Flow rates of 500 gallons

per hour are possible with the system.

Another recovery system design which

requires no power incorporates a floating

skimming head with the selectively transmissive membrane and a suitable container

which are connected, but which may float

independently. The skimming head always

floats at the air-water interface. The

oil which enters the head flows by gravity into the container. The container is so ballasted that the level of oil is always below that on the water surface. By monitoring the height of the container in

the water it can be determined how much

oil has been recovered.

The ultimate objective of the Marine

Pollution Monitoring Symposium is to

reduce the amount of oil entering the

world's streams, lakes and oceans. As

a means to that end, we feel that it is

of utmost importance to provide an early warning of spilled oil and immediate

clean-up. Timely detection and clean-up

is the key to reduction of environmental

damage by petroleum.

Key Words: Oil Detection, Oil Sampling,

Oil Recovery, Selective Membrane.

90
DBS Spec. Fubl. 409, Marine FolluClon Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gslthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

computer file [1] . At present, we have

data for over 100 samples stored in this

data bank.

SAMPLING OF OIL SPILLS AND FINGERPRINTING

BY INFRARED SPECTROSCOPY

Chris W. Brown, Mark Ahmadjian and

Patricia Lynch

University of Rhode Island

Department of Chemistry

Kingston, Rhode Island 02881, U.S.A.

Infrared spectra of crude oils and

their various distillates in the 650 to 1200 cm~l region provide unique fingerprints, which can be used to identify the source of oil slicks. An example of the

differences in the spectra of three No. 2 fuel oils is shown in figure 1. Most No.

2 fuels have the same bands in this spectral region; however, the relative intensities of the bands are characteristic of

each individual sample and these are used

to fingerprint the samples.

A computer data bank has been set up

for petroleum samples from known origins.

Per cent transmission for 21 selected

bands in the 650 to 1200 cm~l spectral

region are converted to absorptivities,

and the absorptivities are stored in a

1200 900

FREQUENCY, CM""

600

Figure 1. Infrared spectra in the 650 to 1200 cm~l region of three No. 2 fuel

oils: a. Delta; b, Zaire; c, domestic.

To match an oil from an unknown origin

with the correct known stored in this data

bank .(assuming that data for the known is

in the data bank) , the spectrum of the un- known is measured, and the per cent transmission for the 21 selected bands are con- verted into absorptivities. A computer

program then performs the following steps:

i) Ratios of absorptivities of each

known to those of the unknown are calculated

ii) Average ratio of each known to unknown calculated

iii) Ratios divided by average to

make average 1.0

iv) Difference between ratios and

1.0 (the average) calculated

v) List the number of bands for

each known with a difference (ratio - average) less than ±0.05, ±0.10, ±0.25 and

±0.50.

In comparing the unknown to the correct

known, the ratios of absorptivities of

known to unknown would have values equal

to or very close to 1.0, since they are in essence the same substance. Deviation

from the value of 1,0 (the ideal average

ratio) for each band gives a measure of

deviation from a "good match" or "positive

identity" of the unknown.

The method has been tested on several

oil slicks during the past year. On one occasion a tanker leaked 100,000 gallons

of No. 6 fuel oil into Narragansett Bay.

A quart sample was obtained from the

tanker. This sample was fingerprinted and

the spectral data stored as a known in the

data bank. Samples were collected from

the Bay and the beaches during the next

four weeks. These were treated as un- knowns in the identification method and in

all cases they matched with the sample

from the tanker [2]. A month after the

original spill a slick (II) came ashore 10

miles from the original spill, and it was reported in the local papers that this

slick was due to the tanker spill. However, our analysis showed that it was from

a different source. Two months after the

tanker spill, another slick (III) was sited in Narragansett Bay. Our analysis

showed that these latter two slicks were

from the same origin, and we eventually

found their source. The question arises as to how well the

method works for light fuel oils. It has

been tested on a No. 2 fuel oil which was weathered on a fresh water pond. A local

industry was leaking oil onto a pond

91
through a storm drain system. The industry had 13 different petroleum products

stored at their plant site. The spectrum

of the oil indicated that it was a No. 2 fuel; however, there were three No. 2 fuels stored at the plant. The spectrum

of the pond sample was close to one of a No. 2 fuels found in an old underground

tank. This tank was excavated and several

holes were found in it. Oil had not been

stored in the tank for several years, so

the tank could not be directly responsible

for the present source of oil. Boring

holes were drilled in the area of the

tank, and eventually an underground pool

of oil was located. This pool had built

up over the years, and leaked into the

storm drains. During this investigation

oil was collected from the storm drains by

directing the water over aluminum foil.

During a 24 hour period we were able to collect 20 ml of oil by this method.

Much of our sampling of oil slicks and

floating films has been done by the Al

foil technique [3]. Oil adheres to the

foil and water is repelled. The foil can

be returned to the laboratory, and the

spectrum of the oil measured without re- moving it from the foil.

Currently, the infrared technique is

being tested on all types of petroleum

weathered in floating containers on Narragansett Bay, weathered on sea water

on the roof of our laboratory, and on sea water under artificial conditions in the

laboratory

.

In addition to oil slicks, we are measuring the infrared spectra of oil ex-, tracted from sea water. Spectra of samples as small as 300 ug of oil have been

measured (spectra of 30 ug samples of

laboratory chemicals have been measured,

but at present we have not measured spectra of petroleum in these small amounts)

.

Currently, we are measuring the spectra of

organics extracted from water in a local

pleasure craft harbor. We have been monitoring this harbor all winter, so that the

increased amounts of lubricating oils can

be detected during the summer months.

We have also measured the spectra of

tar ball samples and extracts of tar balls.

The infrared spectra show that the major

difference in tar ball samples is the

ratio of paraffins to aromatics present.

References

:

[1] P. F. Lynch and C. W. Brown, Environ.

Sci. Technol., 7, M23 (1973).

[2] C. W. Brown, P. F. Lynch, and M. Ahmadjian, Environ. Sci. Technol., In Press

.

[3] C. W. Brown, P. F. Lynch and M. Ahmadjian, Anal. Chem. , 4£, 183

(1974)

.

92
NBS Spec, Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

A NEW INFRARED INSTRUMENT

FOR MONITORING OIL FILMS ON WATER

D. E. Wright

J. A. Wright

Wright & Wright Environmental Engineering

16 Braeland Avenue

Newton Centre, MA O2159 U.S.A.

A new infrared instrument for

detecting and monitoring oil films on water surfaces is currently being evaluated and improved in a program funded

by the United States Coast Guard Office

of Research and Development in Washington,

D.C.

The automatic remote detection

device utilizes a technique based on the

infrared reflectance properties _of water

surfaces. As shown in Bramson [1],

water surfaces exhibit unique properties

of infrared reflectance at the 3 micron

spectral region where sharp changes in

reflectance occur due to absorption bands

of water molecules. In this region, a change in reflectance of almost 500^

occurs for a 10^ change in wavelength.

Figure 1 shows the reflectance dropping

from approximately 2^ at 2 microns to a valley of 0.75?^ at 2.7 microns, and then

rising sharply to a peak of k .ifo at 3.07 microns before returning to approximately 2% at h microns

.

I 1 1 1

—I- 1 \ 2 3 4 Wavelength in microns

Figure 1. The spectral reflectance

of water surfaces.

The opinions or assertions con- tained herein are the private ones of the

writers and are not to be construed as official or as reflecting the views of

the Commandant or the Coast Guard at large.

The reflectance spectrum of oil

films differs from that of water surfaces

in an unambiguous manner when viewed in

the 3 micron region. Hydrocarbons do not

exhibit the deep valley at 2.7 microns

and the adjacent sharp peak at J.l microns.

The peak and valley for water surface re- flectance can be expressed as a ratio of

approximately 6:1; the same ratio for oil

film reflectance is approximately 1:1.

By monitoring the infrared reflectance of

water surfaces at the 3'1 micron peak and

the 2.7 micron valley and computing a ratio from these readings, the presence

or absence of a hydrocarbon film can be

immediately detected.

An Infrared Oil Film Monitor con- sists of a transmitter and a receiver.

When the compact instrument is placed

above and perpendicular to the water surface to be monitored, a beam of infrared

light is transmitted to the water surface

and reflected back to the receiver. The

reflected light beam passes through two

optical interference filters m.ounted in

a rapidly rotating filter wheel and the

resulting signals are electronically

processed to provide two reflectance

readings (at the peak and valley described

above) and a reflectance ratio from those

two readings. An alarm is activated when

the normal ratio decreases to a predetermined value indicating the presence of an

oil film on the water surface.

An evaluation program was begun in

early 1973. Testing of the Infrared Oil

Film Monitor was accomplished in both

laboratory and field environments and the

instrument's oil detection abilities were extensively documented [2] . Laboratory

tests verified that the 3 •1/2. 7 micron

ratio did not significantly respond to

changes in water type or to non-hydrocarbon pollutants introduced into the test

pools. However, the ratio consistently

dropped whenever a hydrocarbon film was present on the water surface. Measurements showed that the instrument responded

to hydrocarbon film thicknesses of 0.1 microns or greater.

Effects of the marine environment

on the instrument's performance were tested during several months of continuous

use while mounted six feet above the water

surface on the bow of a 40-foot research

boat. The water surface of a congested

commercial harbor was monitored both while

underway and with the boat docked in the

inner harbor.

The following observations were made on

the performance of the Infrared Oil Film

Monitor in the field. The instrument's

performance was independent of ambient

lighting conditions - operating 2k hours

a day. Oil detection abilities were not

deteriorated by heavy rain, fog, or high

humidity. The instrument did not "false

93
alarm" at fish and vegetable oil films

on the water surface , yet it was not

hypersensitive to trace concentrations of

hydrocarbons almost always present in

commercial harbors . Independent gas

chromatographic analysis verified the

instrument's detection and false alarm

discrimination capabilities in the field

environment

Possible applications for the

Infrared Oil Film Monitor include;

continuous monitoring of water surfaces

at petroleum loading areas , offshore

platforms, and refineries; crisis monitoring of oil spills when weather conditions exclude aircraft surveillance;

detection of polluting discharges for

law enforcement; and scientific research

and surveys

References

[1] B rams on, M. A., Infrared Radiation , translated from Russian (Institute

of Mineral Fuels, Academy of Sciences of the U.S.S.R., Moscow) by.

Rodman, R. B., Plenum Press, New

York (1968)

[2] Wright, D. E. and Wright, J. A.,

Evaluation of an Infrared Oil Film

Monitor, Interim Report No. CG-D51-7^, U.S. Department of Transportation, United States Coast Guard

Office of Research and Development,

Washington, D.C. (November 1973).

Available to the public through

the National Technical Information

Service, Springfield, VA 22151

Key Words; Infrared Oil Film Monitor;

infrared reflectance; ocean pollution

detection; oil film detection; oil

pollution; remote sensing; water surface

monitoring.

94
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

MAPPING AND IDENTIFICATiTM OF OIL ON WATER BY THE USE OF AN AIRBORNE LASER SYSTEM

G. K. Schwemmer and H. H. Kim

NASA Wallops Flight Center Wallops Island, VA 23337 U.S.A.

Airborne laser oil fluorosensor systems have

been test flown both here and elsewhere for the detection of oil on water [1, 2]. Recently there

has been increased interest in developing an ad- vanced model which not only detects but also

performs a broad classification of the target

oils according to their grades. So far a proven

msthod has been to scan the laser induced

enmission spectrum in relatively slow serialized manner at the rate of one cycle per second

using a spectrometer and image dissecting tube

[3]. In order to overcome both problems of spectral and spatial resolutions necessary for

the application from a relatively high speed aircraft, NASA Wallops is investigating the use of

a 500 parallel optical multichannel analyzer

(OMA) for a laser oil fluorosensing technique.

The block diagram of figure 1 pertains to

the NASA unit which has both real time display

for immediate action, and digital tape storage

to use as later reference. The system uses an Avco pulsed nitrogen gas laser. The laser provides a nominal 1 mj 337 nm ultra violet radiation in 10 nsec. The repetition rate of the laser is set at 30 pulses per second as the CMA's data transfer to a mag tape unit requires 33 msec per cycle.

This gating in turn is also driven by the OMA data

cycles and time delayed so as to pick up the re- turn fluorescent signal. With this arrangement,

the system works just as well as in the day time

as it does at ni^t.

Video information is processed in the OMA for

real time CRT display and converted to BCD for 9 track tape storage. Any preset number of scans may be accumulated in the CMV memory buffer before

dumping on tape. Also, the signal information may be subtracted from a background signal before dunping. The whole system is operated from a remote

control to sinplify operation and a 35 mm wide

angle camera photographs the area to be mapped.

The OMA system was calibrated against a NBS

standard tungsten filament lanp as shown in the arrangement of figure 2. A collimated beam of

known intensity was directed toward the receiver,

placed 30 m away and measurements consisted of a

set of readings in continuous accumulation and gated modes.

30 m

Figure 2. Calibration Apparatus

The following table shows calculated sensitivity

of the OMA vidicon tube in the system from the experiments

.

Wavelength Maximum OIA Sensitivity

poly- Telescope chrox-v-z

Scope

H.V. Pulse

Generator

Digital Tape

Recorder

J

PuUe I Generator

Pulse Amp

H.V. wer Supply

Figure 1. Block. Diagram of Airborne Laser Sensor

The receiver optics consists of a 15 cm dia- meter f-3.2 Cassegranian telescope mounted on a

.3 m polychromator. The output spectrum is fo- cused on the face plate of a silicon intensified

vidicon television camera which is gated on for

0.1 to 1 usee by a hi^ voltage pulse generator.

450 nm

475 nm

500 nm

550 nm

575 nm

600 nm

90 photons /count

45

36

4044

42

In reality, one has to take into consideration the loss factor due to the spectro- meter efficiency, therefore acceptable

efficiency figure should be in the order of

100 to 300 photons per count. In order to test the system's capabilities, it was first

tried in the lab. A pan of water was placed

on the floor and the different grades of oil

films were made on this. The laser and

receiver were placed at a distance of 10 to

15 m down the hall, with a large mirror placed

directly above the water pan to deflect the li^t toward the laser sensor. Single cycle

dunps for 10W30 motor oil , 90W motor oil, and

oil with coumarin dye additive are shown in

figures 3 , 4 , and 5 . This data was taken with

a .6 ram slit with a 500 nsec gating pulse width

and the SIT tube voltage of 9 kv across the

tube. These laboratory measurements and calibrations shew that the instrument is capable of

95
Figure 3. Laser Induced Emission from 10W30 Motor Oil

Figure 4. Laser Induced Emission from 90W Motor Oil

Figure 5. Laser Induced Emission from Oil with

Coumarin Dye Additive

fluorescent signal reaching to the entrace slit

of polydiromator would be approximately in the order of 10^ photons in the visible region. The Avco laser delivers about 1.5 x 10 15 photons

of 337 nm per pulse, and the Quantum efficiency

of laser induced fluorescence is taken as .1%. Our experiences with CMA show that rougjily lOS counts are needed for a good spectral signature

in one scan. If the li^t in one pulse is sufficient for a spectral signature, oil spills

as small as 2.7 m across in size can be detect- ed and catalogued from an aircraft traveling at

the speed of 300 km per hour. These performances do seem to meet the requirements set by

law enforcing agencies to determine the type of

oil pollution to use as prosecuting evidence

from aircraft.

Already certain improvements can be visualized over our present CMA system, if the system were to be used for operational purposes:

a) Physical dimensions of the transmitted laser beam and the entrance slit to the polychromator

should be constructed to match the images so that

a maximum signal to noise ratio be attained, b)

Since the emission spectra of oil derivatives

are in broad bands , the present 500 channels output, 0.5 nm per channel resolution, seems to be

almost redundant. The total fluorescence counts

can be divided among 20 channels , 10 nm per

channel, and coiiputer aided pattern recognition o the peak and shoulder channels can be performed

instantaneously on-board. This problem we believe is srrictly software nature, c) In order to increase further gain on the sensitivity, it is possible to use a higher gain SIT tube available

on the market today. The final design parameters and other operational details will be

determined only after the completion of exten- sive airborne field tests of this system. It is our intention in this presentation to show that such a technique can be available for global oil

surveillance in the near future.

References

:

[1] Kim, H. H., Hickman, G. D., An Airborne Fluorosensor for the Detection

oF Oil on Water , Proceedings of Hydro

graphic Lidar Conf . , Sept. 12, 1973,

Wallops Island, Va., NASA SP 1974.

[2] O'Neil, R. A., Davis, A. R. , Gross,

H. G., Kruus , J., Remote Sensing Laser

Fluorometer , Proceedings of Hydrographic

Lidar Conf. , Sept. 12, 1974, Wallops

Island, Va. , NASA SP 1974.

detecting different grades of oils at shorter

distances. For the radiative transfer equation

of lidar. Power Received = (Area of Receiver) (Power Transmitted) (Q.E.) , (Range)

one would expect that at 100 m altitude, the

[3] Private Communication with H. Ingrao,

D.O.T. - Transportation Systems Center,

Canbridge, Ma,

Key Words: Airborne Laser Oil Fluorosensor,

Remote Detection, Spectral Signatures.

96
NBS Spec. Publ. 409, Marine Pollution MonlLoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

MOVEMENT OF SPILLED OIL IN SAN FRANCISCO BAY AS PREDICTED BY

ESTUARINE NONTIDAL DRIFT

T. J. Conomos

U. S. Geological Survey

Menlo Park, CA 94025 U.S.A.

Introduction

From March 1970 through April 1973,

the U. S. Geological Survey released surface and seabed drifters ev,ery 2 months

within San Francisco Bay and on the continental shelf of central California as a part of a study of seasonal nontidal drift

patterns in the Bay (fig. 1) . One of the

routine release points was located at the

site of a major oil spill which occurred

on 18 January 1971 when two oil tankers

collided at Golden Gate, San Francisco Bay,

California (fig. 2) . Approximately 3200 m3

(26,700 barrels) of Bunker C fuel oil

spilled into the bay [1] . Marked similarities between the

drift patterns of the spilled oil and that

of both the surface and seabed drifters

became immediately obvious. These similarities, together with 3 years of data

from the drifter study made it possible to predict the movement of spilled oil.

Figure 1. The San Francisco Bay region

and environs. Suisun, San Pablo, and

San Francisco Bays constitute the bay

system. North, central, and south bay

designations are also commonly used.

Figure 2. Approximate distribution of oil

slick between 3 and 5 hours after the

collision. The collision point and

anchor location of leaking tanker is

indicated. U. S. Coast Guard observations; redrawn from [4], page 130.

Water depths expressed in fathoms.

Drifter Movements

The drifter used in these studies is

a saucer-shaped plastic disc on a plastic

stem [2] . The drifters float just under

the water surface and consequently follow

the surface currents (surface drifters)

.

With the addition of a brass weight the

drifters become seabed drifters and move

with the near-bottom water [3] . More than

40,000 drifters have been released;

usually 20 to 25 percent are recovered

from each release.

Preceding and following the January

1971 oil spill, drifter movements in the

estuary and adjacent ocean during December

1970-February 1971 (figs. 3 and 4) portrayed typical winter nontidal drift

conditions of near-bottom and surface

waters [3] . There was well-defined estuarine circulation in north bay and in the

Gulf of the Farallones (figs. 3 and 4). In north bay the near-bottom drift

convergence occurred in the shoals in the

vicinity of Point Pinole. South bay ex- perienced a surface drift northward out

through Golden Gate , and a weak near- bottom drift southward in response both

to density-induced circulation and to occa^

sional southeasterly winter storm winds.

Seaward, the north-setting Davidson

Current was well developed (fig. 4)

.

97
Figure 3. Release and recovery points for

seabed drifters in the bay system and

adjacent Pacific Ocean. Drifter move- ments are shown as arrows drawn from

release points to recovery locations

and portray simplified paths of movement; 1200 released and 15 percent

recovered within 2 months. Modified

after figure 5 in [3] .

Figure 4 . Release and recovery points for

surface drifters in the bay system and

adjacent Pacific Ocean. Drifter movements are shown as arrows drawn from

release points to recovery locations

and portray simplified paths of movement; 825 released and 33 percent

recovered within 2 months. Modified

after figure 6 in [3] .

The Oil Spill

The oil spill occurred at 0141 PST

during a flooding tide [1,4]; the bulk of

the oil spilled within central bay began

to drift seaward on the following ebb tide

(fig. 2). By 1200 PST, oil had drifted

several kilometers seaward of Golden Gate.

The main slick bifurcated, one portion

drifting southward and the other portion

drifting northward. Seaward of Golden

Gate, oil eventually beached as far south

as Pescadero Point and as far north as Point Reyes. The largest amount of beached

oil was found north of Golden Gate in the

Stinson Beach-Duxbury Point-Double Point

area (fig. 1). Within the bay, beached oil

was observed as far south as the San

Francisco wharf area and as far north as Point San Pablo and Point San Quentin. Oil

that did not immediately drift seaward

remained in the vicinity of Angel Island

for 3 to 4 days, gradually diminishing in

abundance

.

There was evidence that some of the

spilled oil, in the form of plum- or spindle-shaped tarry globules (ranging

from 1 to 3 cm in diameter and as much as

7 cm in length) had sunk. Globules were variously seen moving along the bottom of

the bay and adjacent ocean, surfacing, or washing onshore with succeeding tides.

Further evidence that oil had sunk was provided by staining of seabed drifters by

oil: seabed drifters released 3 weeks before the spill were found oil-stained on oil-free beaches (fig. 5) several weeks

after the spill.

Figure 5. Release and recovery points

for oil-stained seabed drifters. All

drifters were released from 21 to 23

December 1970, and recovered between

18 January and 26 February 1971. No

drifters released during December were recovered oil-stained until 18 January.

98
The spilled oil sank, apparently

after it gained density by loss of its

lighter hydrocarbon fractions by evapora-^

tion and solution [5,6,7] and was mixed

through the water column by the strong

tidal currents and wind. Oil globules,

carried downward because of the water turbulence that extends to the bottom at

Golden Gate, were apparently mixed with

the sandy and gravelly bottom sediments,

and so weighted, remained near the bottom.

These observations have reinforced a growing awareness [5,8,9,10] that spilled

oil can sink.

Correlation between drifter and oil

movements permits prediction with relative

certainty of movements and behavior of oil

spilled in San Francisco Bay at varying

times and locations. The dominant direction of oil drift from any injection point

can be determined from figures 3 and 4. Indeed, figure 4 (figs. 6 and 8 in [3])

is used as a basis for a plan of preparedness in cleaning up future oil spills in

the bay [16] . In addition, prediction of

oil drift at various seasons of the year

can be based on existing drifter studies

[2,3, unpublished data].

Similarity of Drifter and Oil Movements

Trajectories of surface drifters

generally agreed both temporally and spatially with the gross oil dispersion

patterns. Surface drifters released at

Golden Gate and within the Bay system were recovered in coastal areas where the oil

beached. There was also a similarity in

the relative quantity of beached oil and

drifter recoveries: most of the drifter

recoveries made shortly before and after

the spill occurred in areas where the

heaviest concentrations of oil beached.

Data from the stained seabed drifters

not only present additional evidence that

oil sank, but also give some indication of

the probable direction of the movement of

the sunken oil (fig. 5) . Seabed drifters

released in the Gulf of the Farallones 3 weeks prior to the oil spill were found in

San Pablo Bay. The most heavily stained

drifters were found in the vicinity of

Point Pinole, where oil was seen on the

beaches several weeks after the spill.

However, it should be noted that some of

the oil-stained seabed drifters were recovered on sections of beaches that

remained oil-free, suggesting that they were stained by oil at depths. Oil on the

Point Pinole beaches was apparently transported along the bottom by near-bottom

drift, as were the accompanying seabed

drifters. This is suggested by the fact

that the shoreward limit of beaches

stained by floating oil (observed shortly

after the spill) was 16 km to the west,

toward Golden Gate [11].

Predictions

The foregoing presents evidence for

the landward transport of sunken oil by

(nontidal) estuarine circulation. Studies

of the transport of other substances in

estuaries [12,13,14,15] Indicate that

such transport of sunken oil should occur. This process of nontidal water movement

(both seaward surface drift and landward

near-bottom drift) is fundamental in predicting pathways that may be taken by oil

spilled in or adjacent to estuaries.

Future Outlook

This experience in San Francisco Bay

has shown that basic knowledge of water

mass movements in coastal areas is of

paramount importance in predicting spilled

oil dispersal patterns. Our drifter program, although yielding only empirical

answers in the initial stages of the

experiment, has been useful for describing

seasonal currents in coastal waters.

Similar studies would be of great assistance in determining currents in coastal

areas where oil spills may occur. Oil sinking mechanisms (i.e. great

water turbulence and high suspended

particle concentrations as well as evaporation and solution of light hydrocarbon

fractions) are commonly found in nearshore

and inshore waters; this implies that oil

commonly sinks, and that skimming of oil

from the water surface may not guarantee

adequate removal of all spilled oil.

Furthermore, in light of the landward

transport of sunken oil into estuarine

systems, removal of floating oil in the

coastal zone by deliberate sinking (i.e.

powdered chalk, etc.) seems unwise.

References

[1] Dickman, G. H. , (Unpublished), Report

on Major Oil Spill in San Francisco

Bay on 18 January 1971, Caused by a Collision between the M/T Arizona

Standard and the M/T Oregon Standard , Official U. S. Coast Guard report

(1971) 10 pp.

[2] Conomos, T. J., Peterson, D. H.,

Carlson, P. R. , and McCulloch, D. S.,

Movement of Seabed Drifters in the San

Francisco Bay Estuary and the Adjacent

Pacific Ocean, U. S. Geological Survey

Circ. 637B (1970) 7 pp.

[3] Conomos, T. J,, McCulloch, D. S.,

Peterson, D. H. , and Carlson, P. R.

,

Drift of Surface and Near-bottom Waters

of the San Francisco Bay System: March

1970 through April 1971, U. S. Geolog - ical Survey Open File Map , USGS-HUD

Basic Data Contrib. No. 22 (1971)

.

99
[4] U. S. House of Representatives, San

Francisco Oil Spill , Hearings before a Special Subcommittee of the Committee

on Merchant Marine and Fisheries,

Ninety-second Congress, House of

Representatives Ser. No. 92-3 (1971).

[5] Zobell, C. E., The Occurrence, Effects,

and Fate of Oil Polluting the Sea,

Advances in Water Pollution Research , Pearson, E. A., Ed., Vol. Ill, pp. 85-

109, Pergamon Press, New York (1964).

[6] Dean, R. A., The Chemistry of Crude

Oils in Relation to Their Spillage on

the Sea, The Biological Effects of Oil

Pollution on Littoral Communities

[Suppl. to Field Studies, Vol. 2] , Field Studies Council, London (1968)

6 pp.

[7] Pilpel, N., The Natural Fate of Oil on

the Sea, Endeavour 26 , 11-13 (1968)

.

[8] Poirier, A. A., and Thiel, G. A.,

Deposition of Free Oil by Sediments

Settling in Water, Bull. Amer. Assoc.

Petroleum Geol. 25_, 2170-2180 (1941) . [9] Smith, J. E., Ed., Torrey Canyon

Pollution and Marine Life , Cambridge

University Press, London (1968).

[10] Kolpack, R. L., Mattson, J. S.,

Mark , H . B .

, Jr ., and Yu , T . C .

,

Hydrocarbon Content of Santa Barbara

Channel Sediments- in Biological and

Oceanographic Survey of the Santa

Barbara Oil Spill, Physical, Chemical

and Geological Studies , Kolpack, R. L.

,

Ed., Vol. II, pp. 276-295, Allan

Hancock Foundation, Univ. of Southern

California, Los Angeles, Calif. (1971).

[11] U. S. Environmental Protection Agency,

U. S. Bureau of Sports Fisheries and

Wildlife, and California Division of

Fish and Game, (Unpublished) , Standard

Oil Tanker Spill Shore Damage Assessment, Task Force for Shore Damage

Assessment Special Report, San

Francisco, California (1971).

[12] Simmons, H. B. , Some Effects of Upland

Discharge on Estuarine Hydraulics,

Proc. Amer. Soc. Civil Engineers 81

(separate 792) (1955)

.

[13] Inglis, C. C. and Allen, F. H. , The

Regimen of the Thames Estuary as Affected by Currents, Salinities and

River Flow, Min. Proc. Inst. Civil

Eng . 7, 827-878 (1957)

.

I [14] Meade, R. H. , Landward Transport of

I Bottom Sediment in Estuaries of the

Atlantic Coastal Plain. J. Sed. Pe trol.

32, 222-234 (1969) . [15] Peterson, D. H. , Conomos, T. J.,

Broenkow, W. W, , and Doherty, P. C,

(Unpublished) , Location of the Nontidal Current Null Zone in Northern

San Francisco Bay, U. S. Geological

Survey (1974)

.

[16] Smith, F. M. , Developing a Total Oil

Spill Cleanup Capability in the San

Francisco Bay Area, in Proc. Joint

Conf. on Prevention and Control of Oil

Spills , pp. 21-26, Amer. Petroleum

Inst., U. S. Environmental Protection

Agency, and U. S. Coast Guard,

Washington, D. C. (1973).

Key Words: Estuarine circulation, nontidal

drift, oil spills, San Francisco Bay,

seabed drifters, surface drifters.

100
NBS Sptec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

OIL POLLUTION ALONG THE INDIAN

COASTLINE

S.N. Dwivedi and A.H. Parulekar

National Institute of Oceanography

Caranzalem P.O., Goa , India

SUMMARY

Oil in the form of tar balls is

washed ashore along the Indian beaches.

These were first noticed in 1970 (1).

From 1971 to 1973, studies were undertaken along both east and the west

coasts of India to determine the areas,

seasons, and the intensity of deposition of tar balls and their possible

origin. Figure 1.

The size of the tar balls, places

and seasons of deposition vary a great

deal. Therefore, for comparison of

data from selected beaches, duplicate

samples were collected from 0,1 m^ surface at supra, high, mid and low tide

marks and the weight of tar balls was determined and expressed as g/m^.

The extraneous material associated

with tar balls give some indication of

their origin. Therefore, the associated material like debris , plastic beads

and polychaete tubes etc., were also

noted. In addition, the nature of

beach (sheltered or open), its gradient and intertidal exposure were

also measured.

During 1972, the beaches of the

550 kms coastline on the west, from

Ratnagiri in Maharashtra to Mangalore

in Karnataka State were studied.

In Maharashtra of the 7 beaches

studied, 6 had tar deposits. In Goa,

3 beaches - Anjuna, Baga and Calangute - had fresh tar deposits at low, mid and

high tide marks. But in the southern

part of Goa, i.e., at Colva beach no tar balls were seen. In the Karnataka

State, 'rom Karwar to Malpe , of the 11 beaches, examined, 8 had heavy deposition of tar balls at mid and high tide

marks

Along the east coast, during September 1972, 20 beaches in Tamil Nadu were inspected. Of these 7 were sheltered beaches in the Palk Bay and 13 were open beaches north of the Palk

Bay. In the Palk Bay, mostly at the

high tide mark , tar balls in small

quantities were found at 5 beaches

only. North of the Palk Bay, 10 beaches had moderate deposition of tar

balls.

In the Andhra Pradesh, of the 5 open beaches, only 2 had moderate deposition of tar balls. All the 5 beaches

were away from any estuarine influence.

At Point Calimare where the beach

area was large, the tar balls of different sizes were found in supra littoral region. These were solid tar

lumps mixed with sand and were probably

washed ashore during December- January

of the previous year.

In 1973, along the west coast, 60

beaches were studied, of which 58 were

found to be polluted. The details for

each state are given in table I.

A part of the west coast of India,

from Ratnagiri to Karwar, was selected

as a principal sector for repeated

observations. Other beaches located

along the west coast from Bombay to Porbander, and from Calicut to Trivandrum; were kept for single observation.

Similarly, some beaches along the east

coast of India, from Rameswaram in

Tamil Nadu to Ongole in Andhra Pradesh, were studied only once. Repeated co- verage of selected beaches gave the

intensity and seasons of pollution

whereas from the other areas an estimate of the extent to which the Indian

coastline is affected by the deposition

of tar balls could be made.

Table I. Deposition of tar balls

observed during 1 973 in

various maritime states

along the west coast of

Indi a

Guja- , ~

r aKarna- Ker

rat l^^^- takal^ 1 a= tr a Beaches

Observed 5 10 14 11 19

Polluted 5 10 14 11 17

The tar balls were at first noti- h^®^ Figure 2. ced in 1970 at the Vagator beach, Goa. See Figure 3. During 1971, 6 beaches were inspected '^See Figure k. in Goa, of which 4 had tar balls. At the Calangute beach at the supra tidal area the deposition was heavy.

101
In Maharashtra and Goa, tar deposition started during the last week of

May. In the third week of June, all of

a sudden heavy deposition was seen.

The process of deposition was studied at Goa beaches on 23 June, 1973.

Fresh and small tar lumps were first

seen floating in water. With the incoming tide these were washed ashore.

The size of tar balls varied from 1 to

4 mm. At first they were deposited at low tide mark but with the rising tide

they were pushed higher up and ultimately came to lie at the high tide mark.

At Sinquerim which is nearer to Marmugao Harbour, the intensity of deposition was as high as 4,460.0 g/m^ and

along the northern direction away from

Marmugao Harbour, the intensity decreased. The details of deposition

at some beaches are given in table II. Along the Indian coastline oil

pollution in the form of tar balls

occur in many parts. On the west coast

deposition starts with the approach of monsoon season i.e., in the months of

May and June. Along the east coast

tar deposition appears in December and

January

The deposition is not uniform. A-t some places, parts of the beaches in

between the two levels of tar deposition, were completely free from tar. Maximum deposition occurred at the high

tide mark. Sometimes the tar balls were found in soft or melted condition

due to heat and get mixed with sand

and form large lumps(see figures

Table II. Details of tar ball deposition with associated extraneous

material along some selected beaches.

Place of

observation Date Deposition

EHWS HTM MTM LTM

Association

WEST COAST

KARMATAKA

^

Maravanthe

Honavar

G 0 A

^

Ar ambol

Sinquerim

MAHARASHTRA

Deogarh

Ratnagiri

E AST COAST

TAMIL NADU

Mandapam

Vedaranyam

ANDHRA PRADESH

9.8.72

9.8.72

344.8 10.6

18.3 1.9

31.5.73 93.2

23.6.73 4480.0

22.7.72

20.7.72

Myp aud

Ramayap at- tin am

758.8 128.5

247.7 28.

5

7.9.72

11.9.72 120.1

i_ M.S. 12

17.9.72

5.9

1 38.7

6.2

75.5

- Rhizoohora fruits, polychaete

tubes and plastic beads.

2.2 Rhizoohora fruits and polychaete tubes

- Isolated, fresh and soft lumps

Phvsalia and Rhizoohora

fruits

Fresh deposition. Ph ysalja . Lanthina . Rhizoohora , poly

chaete tubes and plastic

beads

Stray deposits mainly found

at HTM.

Old deposition at HTM. Some

unidentified hard black

pieces were also collected.

Old stray deposition at HTM.

See Figure 3. 'See Figure 2.

102
The polychasts tubes, and Rhizo -

p hora fruits which are associated with

tar indicate that its origin is in the near shore areaa. The deposition also

appears to be influenced by estuaries.

Along the sheltered beaches, the density of tar deposition was less.

It appears that tar balls come from the oil wastes and ship spillage

discharged by the ocean going vessels

(2). The degraded products of oil float for sometime or may sink (3). With

the approach of monsoon conditions and

due to changes in coastal circulation

pattern and wind direction they are washed ashore.

The above observations indicate

that at some selected points along

the Indian coast it is important to start a project of monitoring oil

pollution

.

Sampling of tar balls should be

done from coastal stations, oceanic

islands and by research vessels and

fishing trawlers from different parts

of the ocean so as to obtain the distribution of tar balls at the sea surface. Then it would be important

to study the influence of currents, waves and wind pattern which are largely responsible for bringing the tar

balls ashore.

References:

(1) Nair S. Ayyappan, V.P. Devassy,

5.N. Dwivedi & R.A, Selvakumar.

Preliminary observations on tarlike material observed on some

beaches. Curr. 5ci, Nov. 5,

41 , 21 pp. 766-76 (1972).

(2) Zobell, C.E. From Poll.Abs.

Vol. 1(5), 317 (1970).

(3) Reddy, C.V.G. & Singbal , 5.Y.5.

Chemical characteristic of tarlike materials found on the beaches along the east and west

coast of India in relation to their source of origin. Curr.Sci,

Vol.42, No. 20, 709-711 (1973).

Key words: Indian beaches, Oil pollution. Quantitative study. Season,

Source, Tar balls, Tide levels.

Area surveyed for oil deposition along the Indian

coasts during the year 1970-73.

103
Sinquerlm beach, Goa: Tar deposition at different

tide levels during 1973.

Candolim beach, Goa: Tar balls in the process of deposition during July 1973.

Sinquerim beach, Goa: Tar ball deposition at high tide level, during July 1973.

104
Figure 3.

Maravanthe beach, Karnataka State: Tar ball

deposition during July 1973.

Figure h.

Calicut beach, Kerala State: Tar ball

deposition during 1973.

TOPICAL SESSION II.

Oil in Water: Sampling and Anal/tical Methods

107

NBS Spec. Fubl. A09, Marine Pollution Monitoring (Petroleum)

,

Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 197A (Issued December 1974).

SAMPLING ERRORS IN THE QUANTITATION

OP PETROLEUM IN BOSTON HARBOR WATER

A. M. Ahmed, M. D. Beasley

A. C. Efromson, R. A. Kites

Department of Chemical Engineering

Massachusetts Institute of Technology

Cambridge, MA 02139 USA

The petroleum content of many effluents which are discharged into the environment (tanker ballast water and refinery

waste water, for example) is limited by

state or federal regulations. The enforcement of these regulations depends on the

existence of reliable analytical methods

for determining oil-in-water concentration.

Many such methods are available: they

make use of gravimetry [1]; volumetry [2]

;

infrared [3-6] , ultraviolet [7] and fluores- cence [7] spectrophotometry; and gas

chromatography [4,8,9]. Among these techniques, the infrared spectrophotometric

method seems to be the most popular [5]

.

Despite its widespread use, however, there

is no data available on its reliability in

practice. Therefore, the precision and

accuracy of this method have been studied

using the Boston Inner Harbor as the test

case and using two techniques of oil preconcentration; namely, carbon tetrachloride

extraction [1] and polyurethane foam adsorption [10].

Carbon Tetrachloride Extraction . The water

samples (1 liter each)were obtained by submerging an open glass sample bottle upright

to the desired depth and allowing it to fill

These bottles were then sealed with alumi- num foil held secure with a screw cap. All

samples were preserved with 3 ml of concentrated sulfuric acid, refrigerated, and

extracted within 30 hours after being

obtained. Once in the laboratory, the sam- ple was poured into a 21. separatory funnel and 30 ml of carbon tetrachloride was used to wash the bottle from which the sam- ple was removed. This same carbon tetrachloride was then used to extract the water

sample. After 30 sec agitation and a 3 min

settling period, the non-aqueous phase was drained through a funnel containing about

30g of anhydrous sodium sulfate over a glass wool plug and collected in a 100 ml

volumetric flask. This ringing and extraction procedure was repeated twice more. The sod\im sulfate was rinsed with 5 ml of

carbon tetrachloride which was added to the

extracts and the volumetric flask was made

up to 100.0 ml.

Infrared spectra were taken of these

extracts in a 10.0 mm cell with NaCl windows. Solutions were transferred via a pasteur pipette, washing the cell twice

with the solution to^e observed before

filling. Spectra wei^^scanned from 3400

cm~^ to 2500 cm~l usi^g 5 to 10 times

expansion of the perc&mt transmission scale.

The C-H stretching band at 2930 cm~l was used for analysis. The absorptivity at

this wavelength as calibrated with a motor

oil (SAE 30 weight) was 3.39 1 g'^cm"!. A

typical procedural blank corresponded to an oil concentration of less than 0.010

mg/1.

Samples used in the recovery study were produced by adding known weights of the

motor oil to sample bottles which were then

filled about 1/4 full with distilled water

and shaken. Concentrated sulfuric acid

(2.5 ml) was added, the bottles filled with

distilled water and immediately processed

as described above.

Polyurethane Foam Adsorbtion . The foam

adsorbtion method was implimented as described previously [10] . In brief, 10 to

50 liters of sea water were passed through

a foam disk (8 cm diameter, 4 cm thick,

100 pores/in) and then the retained oil was extracted in Soxhlet apparatus with

carbon tetrachloride. This extract was measured as described above. It was found

necessary to clean new disks by Soxhlet

extraction with carbon tetrachloride for

four to six hours in order to reduce blank

analyses to acceptable levels. It has previously been shown that recoveries of

known concentrations of oil were greater

than 85% for those concentrations above

5 mg/1 [10] ; lower concentrations were not

studied [10]

.

Results and Discussion . In order to determine the performance of the carbon

tetrachloride extraction method itself

devoid of any sampling errors , a recovery

study was carried out. Solutions of oil

in water of known concentrations were

prepared as described above and analyzed.

These results are shown in Table I; ex- cluding the one point of lowest concentration, the average recovery is 101% and the

average error is 13%. Therefore, the

method itself seems quite reliable since

Table I. Recovery Study Data

Oil Added Oil Measured % Recovery

6.12 mg/1 5.96 mg/1 97

3.43 3.66 107

2.26 3.10 137

1.85 1.89 102

1.42 1.41 99

1.26 1.14 91

0.74 0.65 88

0.57 0.46 81

0.46 0.57 124

0.34 0.24 71

0.22 0.22 100

0.17 0.16 94

0.14 0.13 93

0.08 0.11 139

0.01 0.03

109
the quantity of oil in the sample bottle

can be determined with relative standard

deviation of less than 15% for concentrations exceeding about 0.05 mg/1.

Samples were taken in replicate from

Boston Inner Harbor at various stations

at two depths: surface (0-5 cm) and subsurface (25-35 cm) . All replicate samples

at a given station and depth were taken

simultaneously (+ 30 sec) and from within

an area of about one square meter. The

analyses of these samples is shown in

Table II. Table II. Oil Concentration in

Boston Harbor Water (mg/1)

Station

number

lA

Surface

(0-5 cm)

631

54407

708

793

ave. 0.816

rel.s.d. a 53%

confid.lim.b 0.4-1.2

2A 0.213

0.030

0.197

0.320

ave. 0.190

rel.s.d. 63%

confid.lim. 0.1-0.3

IC

ave. rel.s .d. confid. lim.

2C

ave

rel.s.d.

confid . lim.

Notes ; a.

b.

c

0.546

0.256

0.306

<0.025

0. 283

75%

0.1-0.4

0.153

0.296

0. 368

0.138

0.239

46%

0.1-0.4

Subsurface

(25-35 cm)

0.029

<0.025

<0.025

0. 394

0.698

0.234

130%

0.0-0.5

0.143

0.089

0.308

0. 072

0.153

72%

0.0-0.3

0.074

0.254

0.096

0.034

0.114

84%

0.0-0.4

0.077

0.060

0. 269

0. 366

0.193

78%

0.0-0.4

relative standard deviation

of a single measurement

90% confidence limits of mean

average relative standard deviation = 75%

The relative standard deviations for

each set of replicates ranges from 46% to 130% with the average being 75%; this

variability is far in excess of the varibiility of the analytical procedure itself (15%) . This error must, therefore,

be associated with sampling from a heterogeneous system such as oil in water.

A model of this oil in water system

will serve to quantitate the natural

variability which is necessary to produce

this observed variability in the measure- ment (75%) . The model assumes that the

oil is coated on, or in some way associated

with, the particulate matter in the Harbor

water and that there are N of these particles per liter of water. If each particle has X milligrams of oil associated

with it, the measured oil concentration C is given by

C = NX (1) and therefore the relative standard deviation Sc of C is approximately

S,= (S2 + si + (2) s2)l/2

where Sjj, S^ and S;^ are the relative standard deviations of the number of particles

N, of the weight per particle X, and of the

analytical procedure, respectively. If it

is assumed that Sn = Sx^ Sq = 75%, and

S^ = 15%; then Sn = Sx = 52%. In other

words, if the density of particles (N) and

the oil per particle (X) have a relative

standard deviation of 52%, the measured

concentration would have a relative standard deviation of 75%. This magnitude of

variability in the natural system seems quite modest considering the polluted

state of Boston Inner Harbor.

A detailed examination of Table II shows that only the lA surface sample differs significantly from all the others.

This sample was taken in an area located

close to an oil unloading complex and on

a day when a light to heavy sheen was observed on the water. With this one exception, the ambient oil concentration observed in this study was less than 0.5

mg/1. Furthermore, the lack of significant differences in Table II, particularly between corresponding surface and

subsurface samples and between different

locations, indicates that the sampling

error effectively obscures the expected

variation in oil concentration due to tides, currents, and depth. Thus one can

pool all 34 data in Table II to obtain an average oil concentration in Boston Harbor

during this study (July and August 1973)

This average is 0.292 mg/1 and the stanard deviation of the mean is 0.0 53 mg/1;

thus with 95% confidence the oil concen- tration is 0.188 to 0.396 mg/1.

Comparative data for the extraction

and foam adsorption preconcentration methods are given in Table III. In all cases

the oil concentration resulting from the

foam technique is the lower of the two values; in fact, it is low by a factor of five on the average. Although there are sampling errors associated with both techniques

(which may well account for the scatter in

the ratios) , it is clear that the foam

technique has a much lower collection efficiency than liquid-liquid extraction and

is, therefore, a less useful procedure.

110
Table III. Comparison of

oil concentrations determined

using different preconcentration

techniques (surface samples only)

.

Station CCI4 Foam

number Extraction Adsorbtion Ratio

IB 84.1 mg/1 7.2 mg/1 11.7

2B 0.10 0.08 1.25

3B 0.21 0.03 7.0

IC 0.283S 0.19 1.5

2C 0.239a. 0.07 3.4

ave. 5.0

a) average of four values (see Table II)

Conclusions . There are, in principle, two

major ways of reducing the large sampling

error that was observed; namely, replicate

samples and larger sample sizes. These

two methods do not, however, have an equal

effect on the overall precision (S^) . To

demonstrate this effect, the following

assumption is made: the number of particles per unit volume (N) is quite small

and, thus, follows a Poisson distribution.

If this is the case, the relative standard

deviation of N is given by

l OOM

Sn = —N— • Therefore, the overall precision resulting

from n replicate analyses is

(3)

^ c ^nN

+ 1/2

+ — ~) n

(4)

One can now see what the effects of

replication and sample size are. In the

extreme, as n becomes infinitely large S'^

approaches zero. However, as sample size

(and thus N) becomes infinitely large,

approaches t (S^ + s£)/n]l/2 which, if

Sjj = 52% and S;^ = 15%, is 54% for a single

analysis. In other words, the overall

precision is limited by the analytical

error (S;^) and the variability of the weight

of oil on the individual particles (Sjj) and, therefore, increasing sample size will

not be worthwhile if these values are at

all high. Increasing the number of replicates, however, directly improves the overall precision by a factor of over that

of a single analysis.

An example may make these concepts

more concrete. For the data reported

above S^, =75%, n =1 we see that N = 3.71

1~1, Increasing the sample size to one gallon (3.785 1.) and analyzing three

samples gives an increased precision of

35%. Keeping the sample size at one liter

but analyzing four samples gives S

' = 75%//4 = 37%. Clearly this latter case is

preferred from a practical point of view

since less total water needs to be transported.

Finally, a few words on the magnitude

of the sampling error as a function of oil

concentration should be said. At high oil

abundances most of the oil is present on

the water as a layer of varying thickness

and relatively little oil is dispersed.

Obviously, the measurement of most interest

is the thickness of the surface oil layer

not the concentration of the dispersed oil

beneath it. In these circumstances, therefore, one would not make an oil concentration measurement as described here. At the

other extreme, very low concentrations of

oil will actually be in solution and the

sampling errors described here will noi. exist [5] . The sampling problem becomes 0 ; much more severe however at intermediate

concentration (^^-0.025 to '\'25 mg/1) and it

is this oil concentration regime which

requires attention to the magnitude of the

sampling error. Acknowledgements . This work was supported

by the United States Coast Guard, Contract

Number DOT-CG-31862-A, and by the M.I.T.

Undergraduate Research Opportunity Program.

References

[1] Solvent Extraction of Organic Matter

from Water, ASTM Standards 1970 Part

23 D-2778-70, 1915 Race Street,

Philadelphia, Pennsylvania 19103 (1970).

[2] Hearn, L. E presented at the 164th

National Meeting of the American

Chemical Society, New York, August 1972.

[3] Simard, R. G. , Hasegawa, I., Bandaruk,

W. , and Headington, L. E. , Anal . Chem.

,

10, 1384 (1951)

.

[4] Jeltes, R.^nd den Tonkelaar, W. A. M.

,

Water Research , 6, 271 (1972)

.

[5] Brown, R. A., Searl, T. D. , Elliott,

J. J., Phillips, B. G., Brandon, D. E.,

and Monaghan, P. H., Proceedings of

1973 Conference on Prevention and Control of Oil Spills, Washington, D. C.

p. 505.

[6] Gruenfeld, M. , Env . Sci . and Tech.,

636 (1973).

[7] Levy, E. M. , Water Research, 5^, 723

(1971).

[8] Jeltes, R. and Veldink, R. , J. Chromatog . , 2_7, 242 (1967).

[9] Jeltes, Vlater Research , 3, 931 (1969);

[10] Schatzberg,. P. and Jackson, D. F.,

U. S. Coast Guard Report No. 734209.9,

Washington, D. C. (November 1972)

.

Key Words: Petroleum- in-water analysis;

Boston Inner Harbor; Sampling errors; Infrared quantitation of petroleum.

Ill
I
HBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

HYDROCARBON CONCENTRATIONS IN SEAWATER ALONG THE HALIFAXBERMUDA SECTION: LESSONS

LEARNED REGARDING SAMPLING

AND SOME RESULTS

Donald C. Gordon, Jr. and

Paul D. Keizer

Department of the Environment

Fisheries and Marine Service

Marine Ecology Laboratory

Bedford Institute of Oceanography

Dartmouth, Nova Scotia B2Y 4A2

Canada

During the last three years, we have been attempting to measure the

extent of petroleum hydrocarbon contamination in seawater off eastern Canada.

Most of our attention has been directed

to an oceanic section between Halifax

and Bermuda (Fig. 1). During nine

cruises, we have tested different

70° 65^ 60^

45' HALIFAX

IS* 1

40" ,— 1800m-''

oj

40- 1

35* la

35'

30°

BERMUDA '

30*

70* 65' . GOFigure 1. Location of the HalifaxBermuda section

sampling and analytical procedures and

have developed methods which we believe

provide fairly accurate data of hydrocarbon concentrations in seawater. We have been using fluorescence spectroscopy

to estimate aromatic hydrocai'bons and

gas chromatography to measure paraffii;

hydrocarbons. In light of the purposes

of this workshop and symposium, I shall

restrict my presentation to our work

using fluorescence spectroscopy, stressing the attention that must be given

to sampling procedures.

Sampling Equipment

Surface film samples are collected

with a device we call a slurp bottle

(modelled after a sampler originally

described by Goerlng and Menzel [1]). A gallon glass bottle is fitted with a one- hole stopper (made of non-f luoresclng

and hexane-resistant material) through

which is inserted a piece of glass tube.

A 30 cm length of flexible (but inert to hexane) tubing which is fitted with

corks along Its length so that it will

float at the sea surface is attached to

the outer end of the tube. A vacuum of

65 cm Hg is drawn and the sampler is

thrown overboard away from the ship Just

as it is stopping on station (before

the surface layer can be contaminated)

.

About 100-300 ml of seawater is drawn

into the bottle from the upper 5 mm

through the tubing in about 15 sec. After filling, the sampler is retrieved

using an attached line.

Shallow samples (1 to 5 m) are collected In glass bottles of 2.281

volume. These are placed in a weighted

metal frame attached to a line and tossed

overboard av;ay from the ship immediately

after slurp samples are collected. A float attached to the line suspends the

glass bottle a given distance below the

seasurface, the Inside of the bottle never comes into contact with the surface

film.

For deeper samples, the best samplers (but not perfect for reasons discussed later) v;e have located are teflon-lined stainless steel Knudson

bottles of 1.25 1 volume. Before using,

all rubber and leather gaskets must be

replaced with teflon and the entire

bottle must be thoroughly cleaned

Inside and out with methylene chloride

(or similar solvent) to remove any

traces of oil and grease (even after

doing this before our most recent cruise,

It wasn't until the fifteenth station

that the bottles appeared to be truly

"clean"). These bottles are lowered

open on a hydrographic wire.

In the earlier stages of our work,

we used 12-1 and 30-1 Niskin bottles

(closed with rubber tubing) to collect

water samples. To our surprise and

grief, we recently learned that the data

obtained using the Niskin bottles are

113
Inaccurate. By conducting a number

of laboratory and field experiments,

we have observed that fluorescing

material in seawater (both raw and

spiked with crude oil) Is quickly

adsorbed to the inner surface of Nlskln

bottles. This process Is reversible

and these compounds can accumulate and

be released to subsequent water samples

collected if the bottles are not

washed with solvent after each use. In our earlier work, we washed the

bottles only with fresh water and isopropanol before and after each cruise,

a procedure that did not remove the

adsorbed material. As demonstrated in

a later section, this adsorbed

fluorescing material was being added

to our samples causing the resultant

concentrations to be erroneously high.

Our experience indicates that all

water samplers must be rinsed with

solvent (hexane or methylene chloride

depending upon the sampler) after each

use to recover any adsorbed material

lost from the enclosed water sample.

Also, the entire contents of a sampler

must be extracted, so samplers must

range from about 1 to 5 1 in volume.

Extraction and Preparation of Blanks

Since the volume of slurp samples

is small (generally 100-300 ml), they can conveniently be extracted with

hexane. After the water is transferred

to a 500-ml glass separatory funnel,

30 ml of hexane is added to the slurp

bottle through the inlet tubing and

swirled around making sure that it comes into contact with the entire

inner surface of the slurp bottle. This

hexane is then added to the water

sample and the extraction performed.

Water collected in glass and

Knudsen bottles is transferred to 4-1

glass separatory funnels. Bottles are then thoroughly rinsed twice with 40

ml of methylene chloride which is then

added to the water and the extractions

performed.

We use methylene chloride in place

of carbon tetrachloride (used by Levy

[2])because of its lower toxicity and

lower boiling point (^O.l'C compared to yS.S^C). Comparison of the two solvents

indicates that using carbon tetrachloride causes about half the fluorescing

material in seawater (both raw and

spiked with fresh crude oil) to be lost,

most probably during the evaporation

step [3]

Frequent blanks must be prepared

by rinsing samplers with solvent

(slurps are first evacuated) and then

passing the solvent through the separatory funnels; the same procedure as with

samples but no water is present.

Merely setting aside a bit of solvent

is not sufficient for a blank.

Laboratory Analysis

Extracts are returned to the

laboratory in glass vials or bottles

sealed with aluminum foil-lined caps.

Extracts should be kept dark to avoid

photochemical reactions (especially

with methylene chloride extracts).

Hexane extracts are analyzed directly;

methylene chloride extracts are evaporated in a rotary evaporator under

slight vacuum and the residue taken up in hexane. Hexane extracts are analyzed

by fluorescence spectroscopy [3] using

the same instrument and similar operating

conditions as Levy [2]. The instrument

is calibrated dally with Venezuelan

crude oil. For convenience, the data

are reported in units of crude oil

equivalents. It must be remembered

that the observed fluorescence may not

be due to petroleum hydrocarbons and

the actual concentration of any naturallyoccurring fluorescing material could be

much different than the crude oil

equivalent concentrations.

Results

The results obtained using these

procedures on our most: recent cruise are presented in Table 1. Concentrations

are greatest in "the surface film and

drop quickly with depth in the upper

5 meters. There were no apparent

Table I. Concentrations of hydrocarbons

(crude oil equivalents) detected in seawater along the

Halifax-Bermuda section in

April 1974 as measured by

fluorescence spectroscopy.

yg/1

Sampler Depth n Mean

Standard

Deviation

Slurps l-5mm 53 9.,28 18.38

Glass

bottle

Im 23 0,.56 0.58

Glass

bottle

5m 24 0,.37 0.42

Knudsen

bottles

lO-lOOOm 50 0,.79 0.69

Knudsen

bottles

10-lOOOm

1 15 0,,81 0. 81

' lowered and retrieved open

,

no water

collected.

114
regional differences In concentration at any depth. Concentrations at 10 m and

deeper (collected with Knudsen bottles)

are greater than at 1 and 5 m (collected

with glass bottles). This appears to be

an artifact for when Knudsen bottles are lowered and retrieved open similar con- centrations are obtained (Table 1).

Therefore we conclude that there is

little if any fluorescing material in

seawater deeper than 10 m along the

Halifax-Bermuda section. The measurable

fluorescence obtained from Knudsen

bottle samples must represent 1) underestimating blank values, 2) material

emanating from the hydrographic wire,

or 3) material picked up by the Knudsen

bottle as it is lowered open through

the surface film. The greater concentrations observed by us earlier using Niskin

bottles (Table 2) are apparently the

result of contamination.

Table II. Erroneous hydrocarbon concen- trations (crude oil equivalents) observed along the

Halifax-Bermuda section when

samples were collected with

Niskin bottles (October 1971-

October 1973)

yg/1

Depth

(m) n Mean

Standard

Deviation

1-10 307 2.75 2.2

11-100 497 2.60 2.3

101-1000 159 2. 36 2.0

>1001 64 2.12 2.2

surface film. The large standard

deviation indicates that the distribution is quite spotty.

2. The entire volume of seawater collect

ted in a sampler must be extracted

and the sampler must be rinsed with

solvent after each use to recover adsorbed material.

3. The inner surface of samplers being

lowered to sub-surface water must not come into contact with the surface

film.

4. Deep water samples for hydrocarbon

analysis must be collected with a device like the organic free water

sampler designed by Dr. Max Blumer

and manufactured by Benthos, Inc.

5. A monitoring program such as is being

planned is of no value unless sampling

and analytical procedures are thoroughly tested, discussed and cross-checked

before it begins. Too often we let our desire for data blind us from

faults in our methods.

References

[1] Goering, J. J. and D. W. Menzel,

Deep-Sea Res . 12, 839-843 (1965)

[2] Levy, E. M. Water Res . 5, 723-733

(1971). ~

[3] Kelzer, P. D. and D. C. Gordon, Jr.,

J. Fish. Res. Board Can . 30, 1039-

1045 (1973).

Conclusions

1. Petroleum hydrocarbon contamination

in seawater along the Halifax-Bermuda

section appears limited to the upper

few meters. Most is contained in the

Keywords: Oil pollution, petroleum or aromatic hydrocarbons in sea- water, water sampling,

fluorescing material in sea- water, fluorescence spectroscopy.

lis

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS , Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

DETERMINATION OF AROMATIC HYDROCARBONS

IN SEA WATER

USING AN ELECTROLYTIC STRIPPING CELL

S. P. Wasik and R. N. Boyd

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234 U.S.A.

This paper describes a head-space

method for determining aromatic hydrocarbons in sea water. The hydrocarbons

are stripped from sea water, under equilibrium conditions, by very small bubbles of

hydrogen gas generated electroly tlcally

from a gold electrode located at the bottom of a cyllndrlcally shaped cell. The

hydrocarbon concantratlon In the sea water

Is determined from the volume of the sea water and the hydrocarbon concentration in

the head-space after a measured volume of

hydrogen has bubliled through the stripping

cell.

Figure 1 shows a drawing of a typical

stripping call. The large compartment (A)

has a volume of 1000 ml. The small com- partment (B) has a volume of approximately

200 ml. The two compartments are connected

by a 35-mm OD glass tube with a 30-mm ID coarse porosity glass frit (C) at one end.

On the small compartment side of the frit

is a silicic acid plug. The two gold

electrodes (1-mm OD wire) were held in

each compartment by means of a septum

located in a 1/4 x 1/4-inch union fitting.

The electrode (D) in the large compartment

has a spiral configuration to provide a

large surface area. The hydrogen headspace was sampled by a gas sampling valve

thermostated at 100°C. The chromatographic column was a 15.24 x 0.508 mm ID. SCOT prepared with finely ground diato- maceous earth plus fused silica support

and coated with a mixture of m-bls(mphenoxyphenoxy ) benzene and Apiezon L.

A constant current device provides

the electrical current to the stripping

cell. The volume of hydrogen, V, bubbled

through the large compartment is calculated from the equation:

V It/F • 11,207 T /273.15

c (1)

where 1 is the current, t the time in

seconds, F the Faraday constant and T^. the temperature of the stripping cell.

Theory

Consider a measured volume of sea water in a cyllndrlcally shaped vessel

containing a gold electrode at the bottom

of the cell. Connected to this vessel by means of a glass fritted disc is a smaller

cyllndrlcally shaped vessel containing a gold electrode and an aqueous solution of

sulfuric acid. When an electrical current

with the appropriate polarity is allowed

to flow through the cell, hydrogen, in the

form of very small bubbles, is evolved at

the gold electrode in the large vessel

while oxygen is evolved from the gold

electrode in the small vessel. The dissolved hydrocarbons in the sea water come

to equilibrium with the hydrogen bubbles

and their concentration is measuied by gas chromato gr aphy

.

If one assumes that the concentration

of a particular hydrocarbon in the hydrogen leaving the cell is proportional to its concentration in the sea water one then has the relation:

C^(V) S^(V)/K^ (2)

where C^CV) is the hydrocarbon concentration in the hydrogen, Sj^(V) is its concentration in the sea water when volume, V,

of hydrogen has passed through the sea water, and 1/K^ is the proportionality

factor. If there is equilibrium, K will

be equal to the partition coefficient.

One can show that the ratio of Ci(V) to its value, Cj^(O), at zero hydrogen volume

is given by the expression:

ln(C^(V) /C^(0) ln(S^(V)/S^(0))

= -V/KV.

(3)

Figure 1. Electrolytic Stripping Cell.

where Vl is the volume of the sea water

and S^CO) is the concentration of a particular hydrocarbon in the original

sea water.

117
The fraction of the total amount of

a particular hydrocarbon, S±(V)/S±(Q),

extracted by a given V/V^ of hydrogen

depends upon the magnitude of K^. For

the case of gasoline dissolved in sea water at 80°C we observed that 95% of

the aliphatic and oleflnic and only 0.4%

of the aromatic hydrocarbons are extracted

when V/Vl is equal to 0.046. Thus the

aliphatic and olefinic hydrocarbons are quickly stripped from the cell for low

values of V/Vl leaving a large fraction of

the aromatic hydrocarbons in solution.

After the aliphatic and olefinic hydrocarbons are stripped out of solution, the

concentration of the aromatic hydrocarbons

can be measured for different V values.

From the plots of InCi(V) vs. V/Vl the

slope 1/K-L and Intercept InCj^(O) is

obtained for each hydrocarbon. The aro- matic hydrocarbon concentrations in the

original sea water can then be calculated

from the expression 5-^(0) = KiCi(O). Once

the K's for the aromatic hydrocarbons are known, Sj^(O) may be determined from the

express ion :

S^(0) = C^(V)K^ exp (V/V^K^). (4)

In this case only one value for C^CV) is

required

.

For the case of gasoline, we added

0.05 ppm toluene-dg as an internal standard to 1000 ml of a dilute aqueous solution of un-leaded gasoline. The diluted

extract was poured into a 1000 ml stripping cell located in a constant temperature water bath. The temperature of the

water bath was raised to 80°C and 0.3

amperes of current were passed through the

cell. The upper chromatogram shown in

Figure 2 was obtained by sampling 1 ml of

the head-space after 30 ml of hydrogen had

bubbled through the stripping cell. This

chromatogram shows the large number of

aliphatic and olefinic hydrocarbon peaks

that are eluted. At the same time the

early aromatic hydrocarbon peaks are also

eluted. The lower chromatogram in Figure

2 was obtained after 46 ml (V/Vl = 0.046)

I !_ l__ I L- 0 5 iO 15 20 25 30

TIME (m!n)

Figure 2. Chromatograms of the head-space

gas showing the aliphatic, olefinic, and

the early aromatic hydrocarbons eluted

after 30 ml of H2 gas bubbled through

the cell (upper) and the aromatic hydrocarbons eluted after 46 ml of H2 gas bubbled through the cell (lower).

of hydrogen had bubbled through the cell.

All the aliphatic and olefinic hydrocarbon

peaks are absent from this chromatogram.

The head-space was sampled three other

times at different V values and the peak

areas were measured with an electronic

integrator. From the log Cj(V) vs. V/V^

plots the slopes, 1/Kj^'s, and intercepts,

C±(0)'s, were determined. The amount of

each aromatic hydrocarbon in the original

solution was calculated from equation 4. Acknowledgement: This research was supported in part by the Office of Marine

Technology, Maritime Administration.

Key Words: Head-space; Electrolytic

stripping cell; Aromatic hydrocarbons;

Partition coefficient; Sea water.

118
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

DETERMINATION OF AROMATIC AND TOTAL

HYDROCARBON CONTENT IN SUBMICROGRAM

AND MICROGRAM QUANTITIES IN AQUEOUS

SYSTEMS BY MEANS OF HIGH PERFORMANCE

LIQUID CHROMATOGRAPHY

A, ZSOLNAY

Bermuda Biological Station for Research

St. George's West, Bermuda.

In order to determine the hydrocarbon concentration in small water

samples (under 51) rapidly and fairly

simply, two separate but related

methods were developed [1, 2] . Both

are based upon the use of high performance liquid chromatography. They are more sensitive than the IR methods,

which tend to have a maximum sensitivity

of 0.05 mg [3], and they are probably

more specific than UV or fluorescence

methods used without column chromatography [4] . Their main advantage over

GLC lies in the fact that they are simpler and more rapid for the obtaining

of quantitative results [5]

.

For the extraction of hydrocarbon

material from the aqeous system, a liquid extraction method is used, since

it is the simplest and most direct

method. It also has the advantage that

blanks can easily be prepared. The solvent used to extract the hydrocarbons

is 1,2,2-trichlorotrifluoroethane (TCF)

.

It was found to have several advantages.

It is a virtually non-polar compound

that is not a hydrocarbon. It is heavier than water, which enables it to be

removed simply with a pipette from the

bottom of the extracting vessel, and it

boils at 47.6°C, enabling it to be con- centrated quite readily. In addition

it is transparant to UV light at 254 nm.

PRESSURISED SOLVENT CONWWER

WASTE CONTAINER AMBIENT BATH Figure 1. Liiyout of the high performance liquid chromatography system used

to detect the total hydrocarbon content.

The tubing has an O.D. of 1/8 in. and

the ambient bath a voliome of about 12 1.

Ten ml of TCF are added to each liter

of water to be extracted and shaken for

about 5 min. and then allowed to stand

for 10 min. to permit the phases to separate. The extract is then removed

with a pipette and concentrated down to

about 1 ml or so under vacuum. Afterwards it is placed in a special concen- trating tube, which is simply a small

test-tube that has part of a sealed

pipette with 10 yl gradiations fused on

it so that the amoxint of extract that

remains after concentration can be read

with an accuracy of 5 yl. This final

concentrating phase is done with a stream

of molecular sieve cleaned nitrogen until

the extract was reduced to 100 yl. The

concentrating procedure is by far the

most time consuming and the most prone

to contamination, making it absolutely

essential that blanks be run. The apparatus used to determine the

"total" hydrocarbon content is shown in

figure 1. The flow calorimeter, which

is used to detect the hydrocarbons is

shown in figure 2

.

FROM COLUMN EFFLUENT

REFERENCE CELL THERMISTOR TOP

PLATE

BOTTOM

PLATE

TO WASTE CONTAINER

Figure 2. Diagram of the flow calorimeter used. It is an adsorption

detector, with the detector cell thermistor embedded in a material that is

capable of adsorbing hydrocarbons.

It roughly operates on the following

principle. Tv70 thermistors are in the

solvent stream, and one of them is

embedded in a substance that is capable

of adsorbing hydrocarbons . As long as there is no material coming off the

column, the circuit is balanced. However, when material comes off the column,

it is adsorbed on the adsorbent surrounding one of the thermistors. The heat

of adsorption that results, also

produces a change in the resistance of

the thermistor, which then leads to an imbalance in the circuit and a peak on a recorder. This process is reversible

and a peak in the opposite direction to

the first one results right afterwards

as the material is being desorbed. The

adsorbent that is used is porous glass

beads with a pore size between 3.0 and

4 . 5 nm.

119
The column that is used in the system

to separate non-hydrocarbons from the

hydrocarbons has an I.D, of 1.8 mm and

is 5 cm long. It is filled with 10%

deactivated silica gel. The resulting

system was found not to produce any

response even with such slightly polar

substances as stearic acid n-decylester

or methyl palmitate. The saturated hydrocarbons were all found to have a response

between 76 to 110% of n-nonadecane, which

was used as the standard throughout.

Unsaturation decreased the response per

unit weight. This decrease was minor

among the mono-unsaturated compounds, but

quite strong among the poly-unsaturated

alkenes such as carotene and sgualene.

The former produced no response, and the

latter had a response that was 32% of

nonadecane ' s. This means that this method will tend to underestimate the hydrocarbon content when there is a large

proportion of unsaturated compounds

present. If one assumes that 50% of

the hydrocarbons present are unsaturated

and that the unsaturated hydrocarbons

have, on average, a response per unit

weight that is 50% of that of nonadecane,

the value determined will be 25% too low.

This is naturally only a very rough estimate, but even under these extreme conditions, one can see that the underestimation is still at a tolerable level,

when one considers the complexity of the

problem of measuring hydrocarbons in the

aquatic environment.

Aromatic hydrocarbons will also be

underestimated. Naphthalene, for

example, has a response that is only 29%

of that of nonadecane. However, their

contribution to the total hydrocarbon

content in non- stagnant and not severely

polluted water is very low [5] , quite

likely well under 10% [7].

The smallest amount that can readily

be ietected is 2.0 + 1.7 yg, based on

non:"decane. The high standard deviation

is cue to poor reproducibility in both

the extracting and the concentrating

phase.

For the determination of the aromatic

hydrocarbons , the same extracting and

concentrating procedure is used as above.

The apparatus is somewhat different in

that a UV detector, which measures

absorbance at 254 nm, replaces the flow

calorimeter and the ambient bath is not

needed. A longer column (10 cm) with

more active (2% deactivated) silica gel is

also used, since aromatic hydrocarbons

are somewhat polar and more care must

be taken to assure their separation

from other weakly polar compounds

.

The chief disadvantage in the use of a UV detector lies in the fact that the re- sponse per unit weight varies enormously

from compound to compound. As a result

all values can only be given relative to

a standard and will vary greatly dapiri'i"

ing upon the standard selected. A ai.m- ilar procedure is often used in measuring

the proteins in aquous systems where albumin is usually the standard. It was decided that phenanthrene was probably the

best choice here, because of its "inuermediate" size among the possible aromatic

hydrocarbons. Benzene is not suitable.

„

since one can assume that most of thi

benzene compounds are lost during the con- centrating, because of their relatively

low boiling point. If naphthalene i-> used as a standard, all the values found

will be larger by a factor of about 10,

since naphthalene absorbs at 254 nru only

about 0.1 times as well as phens.iithrene.

One indication, however, that ph'inanthrene is a suitable choice -.hat almost

all the samples that were me. red in the sea by the author had a ret^i t.r.on time

that was intermediate betwe'.;.. that of

phenanthrene and naphthalene tending to indicate that the majority the aromatic

compounds were substituted 3 ring ones. Nevertheless, caution must be used in

interpreting the quantitative data

obtained until a final definitive

standard has been selected.

Due to the extreme sensitivity of the

UV detector, only 20 pi of the concen- trated extract needs to be injected. The

smallest amount of material, based upon

phenanthrene, that could readily be detected was 4 + 10 ng. Again, the high errors in the extracting and concentrating procedure are responsible for the

large standard deviation. In order to

minimize its effect, sample sizes should

be as large as possible. Both these methods have been successfully used at sea [7].

References

[1] Zsolnay, A., Chemosphere 6, 253-

260 (1973).

[2] Zsolray, A., J. of Chromatography

90, 79-85 (19741";;

[3j Carlberg, S. R. and Skarstedt, C.B.

,

Cons . Int. Explor . Mer 34 , 506-515

(irt72) .

[4] Levy, E.M., Water Res. 5, 723-733

(1971)

.

fi] Jhrhardt, M. and Blumer, M.

,

Environ. Pollut. 3, 179-194 (1972).

[6} Meinfchein, W. G, , HydrocarbonsSatv.rated, Unsaturated and Aromatic,

in Organic Geochemistry , Eglinton,

G. ard .w.urphy, I'. , Eds. pp.

:30--<57, Spring -.r ^'t.rlag, New York,

Berl-;.n - 969) .

[7] S&olna/, A., Paper presented at

1373 Meetirg of the International

Council for the Exploration of the

Sea. CM. 1973/E;22 (1973).
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Froceedlugs of a Symposiura and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

DETERMINATION OF Ci-Ciq

HYDROCARBONS IN WATER

Clayton D. McAuliffe

Chevron Oil Field Research Company

La Habra, California 90631 U.S.A.

Several fields require the measurement of widely varying concentrations of

hydrocarbons dissolved in water. These

fields include environmental studies,

petroleum exploration, and biochemical

research, among others. The method re- ported here is based on successive gas chromatographic analyses after repeated

equilibrations of a hydrocarbon-free gas

with an aqueous sample containing dissolved hydrocarbons. All classes of

hydrocarbons having up to 11 carbon atoms

in the molecule can be determined.

EXPERIMENTAL METHOD

Sample Collection and Preservation

It is desirable, if possible, to ana- lyze the aqueous sample for hydrocarbons

at the time of its collection. In many

cases, however, this is not possible. A sampl e, therefore, shoul d be collected in a glass container, tightly sealed with a minimum gas space over the water, and having only teflon in contact with the water.

A bactericide must be added to the water

prior to sealing to prevent bi odegradati on of the hydrocarbons.

Laboratory Measurements

Typically, a 50-ml glass hypodermic

syringe (with Luer-Lok fitting and an appropriate valve) is flushed several

times with portions of the aqueous sample

of which 25 ml is finally retained.

Twenty-five ml of helium (nitrogen, air or other hydrocarbon-free gas) is added and

the syringe capped. It is then vigorously

shaken on a paint shaker for 3-5 minutes

or approximately 20 minutes on a laboratory wrist action shaker to establish

equilibrium between phases. Twenty to 23

ml of the gas phase is then flowed through

the sample loop (previously flushed with

helium) of the gas chromatograph , and then

a measured volume, usually from 1-10 ml of

the gas is introduced for analysis.

The remaining gas in the syringe is carefully discharged by moving this solution to the syringe tip, and 25 ml of

fresh helium is added. The equilibration

process is repeated as many times as is required for the specific application.

The reader is referred to the original

publication [1] for details of the method.

Wasik and Brown [2] have modified the

technique to permit automation and con- stant temperature conditions.

A plot of the log of the hydrocarbon

concentration in the gas phase versus the

number of equilibrations produces a straight line. From the semi-log line

read any two adjacent gas phase concentrations. Divide the greater by the lesser

and subtract 1. This is the distribution

coefficient. Note the intercept of the

line, divide it by the distribution coefficient, and one has the desired concentration in the original sample after cor- rection for instrument response and sample

size.

Partitioning of Hydrocarbons

Different classes of hydrocarbons

partition differently between water and

gas phases based upon their solubilities

in water and their vapor pressures. Thus,

the different distribution coefficients

permit the separation of the various hydrocarbon types. Figure 1 graphically demonstrates the way that different classes of

hydrocarbons partition. The original solution was formulated in tap water to give

approximately the same peak heights for

benzene, cyclohexane, and n-hexane following the first equilibration. The second

equilibration resulted in a small n-hexane

peak, the cyclohexane peak reduced approximately 90%, and a toluene peak reduced by

3rd

1

EQUILIBRATION

\8= 2nd si

EQUILIBRATION Sis —

LU TOLUENE CO

J \ NORMAL HEXANE

1st

CYCLOPENTANE

IMPURITY EQUILIBRATION

1 J ,

Figure 1. Partitioning of three different

classes of hydrocarbons between equal

volumes of tap water and helium at 25°C for successive equilibrations.

121
approximately 20%. The third equilibration shows no n-hexane peak, a very small

cyclohexane peak, and toluene as the major

hydrocarbon remaining.

Olefin and acetylene hydrocarbons

would distribute between the water and gas phase with different distribution coefficients. If present in the water sample,

they could be identified and measured.

The percentages of total hydrocarbon in the gas phase calculated from solubilities

and vapor pressures [3,4] (for equal volumes of gas and distilled water) for 1- pentene, 1 ,4-pentadiene , and 1-pentyne are

94, 83, and 51 respectively.

Because alkanes have low solubilities

in water compared to their vapor pres- sures, 96+% of them partition into the gas phase when equal volumes of gas and water

are equilibrated. Thus, analysis of the

first equilibration is sufficient to determine alkane concentration in the water

phase except for the most precise determination. If higher accuracy is required,

the concentration in the gas phases of the

first two equilibrations can be summed.

Cycloalkanes partition less into the

gas phase than do alkanes. Figure 2 shows

that after 3 equilibrations, cyclohexane

had been 99.7% transferred to the gas phase

.

10000 E 1 1 1 1 r

3

EOUILIBRATION NUMBER

Figure 2. Partitioning of cyclohexane

between equal volumes of tap water

and helium at 25°C for successive

equi 1 i brati ons

.

Aromatic hydrocarbons remain principally

in the water phase when equal volumes of

water and gas are equilibrated. Fii,ure 3 shows the actual data points for repeated

equilibrations of toluene with waters of

varying salinity. It is apparent that

unless the water is highly saline many

equilibrations would be required to remove

the majority of the toluene. Therefore,

the most convenient method for determining

the original concentration is to fit a straight line to the data points and back

extrapol ate

.

Figure 3. Partitioning of toluene between

equal volumes of three salinity waters

and helium at 25°C for successive

equi 1 i brati ons

.

One of the principal advantages of

this method is its ability to determine

hydrocarbon concentrations accurately in

solutions of varying ionic composition.

It matters little whether the water is fresh, brackish, sea water, or subsurface

bri ne

.

Separation from or Identification

of Non-Hydrocarbon Organic Compounds

The method gives good separation of

hydrocarbons from highly water-soluble

organic compounds such as alcohols, aldehydes, ethers, and acids. Because of the

high water solubilities of these organic

compounds, the distributions are highly

favored toward the water phase, and little

of them is found In tne gas phase. If the

water phase should contain a sufficiently

122
high concentration of an organic compound gave a distribution coefficient that duplifor it to appear in the gas phase, then the cates that for chloroform (as calculated

gas phase concentration decreases very from solubility and vapor pressure data),

slowly with successive equilibrations. Confirmation was made by adding chloroform

Such distribution coefficients, along with to water and analyzing. Benzene and tolurelative retention time, help identify ene were identified also by relative retenunknown organic compounds. tion times and distribution coefficients.

Method Sensitivity This drinking water supply was monitored almost daily for an 18-month period

When we use the described procedure and the concentrations observed are repreand introduce a 5-ml gas sample into the sentative of that time period. The concen- chromatograph , the method is capable of de- trations are: chloroform 8-10 ppb, benzene

tecting alkane and cycloalkane hydrocarbons 2-3 ppb, and toluene 0.2 ppb. Recently

in water if they are present in amounts of Nov^k et al [5] report benzene and chloro1-3 parts in 10l2 parts of water by weight, form in pure drinking water in CzechosloAromatic hydrocarbons, because of their vakia, but concluded that the contamination

lower partitioning into the gas phase, can of the drinking water with these compounds

be detected if present in concentrations of took place during manipulation in the labo4-12 ppt. Reasonable accuracy can be ob- ratory. The results reported in figure 4 tained if the aqueous concentrations are were observed at the same time sea water

20-30 times these values. samples were being analyzed; the latter

contained only methane. Thus, laboratory

APPLICATIONS OF THE METHOD contamination did not contribute to the

compounds shown in figure 4, and chloroform

Contaminants in Drinking Water ' and benzene may have been in the water re- ported by Nov^k and coworkers.

An actual example of the indentification of organic contaminants in a tap water Environmental Surveys

sample from a city water supply is shown in

figure 4. Another advantage of the gas equilibration technique is that no sample manipulation or sample preparation is required.

The sample can be analyzed immediately upon

collection. This was done in a study of

water samples in the Cook Inlet [6]. A gas

chromatograph was placed aboard the University of Alaska, Institute of Marine Science's research vessel. Water samples were collected from near surface, mid-depth, and near bottom from some 60 stations throughout the Cook Inlet. At all stations and

all depths only methane was observed in the

sea water, and it appeared to be in approximate equilibrium with methane in the

atmosphere.

During and immediately following the

Chevron oil spill in the Gulf of Mexico,

[7] water samples were collected at near surface, mid-depth, and near bottom for a large number of stations in and surrounding

the spill area. Only in those waters known

to have emulsified crude oil were measurable hydrocarbons observed using the gas

equilibration technique. The highest total

dissolved hydrocarbon concentration was 0.2

ppm. The dissolved constituents were principally low-molecular-weight aromatic hydrocarbons .

Partitioning of Hydrocarbons Between

The Atmosphere and Natural Waters

Figure 4. Organic contaminants in tap When oil is discharged onto a water

water from a city water supply. surface the lower-molecular-weight hydrocarbons with up to at least 12-15 carbon

The first peak is predominantly meth- atoms in the molecule evaporate into the

ane and/or other low molecular weight atmosphere rather quickly [8]. Portions of

alkanes and olefins. The next prominant the lower-mol ecul ar-wei qht hydrocarbons

peak has the relative retention time for also dissolve in water t7]. The amount of

n-hexane, but the additional equilibrations dissolved hydrocarbons is generally low.

X8

METHANE, HHANE.

ETHYLENE /

CHLOROFORM

BENZENE

I NON-HYDROCARBONS

--CHLOROFORM

EQUILIBRATION 1

BENZENE NON-HYOROGARBONS

TOLUENE

CHLOROFORM

BENZENE

NON-HYDROCARBONSxlJOLUENE

EQUILIBRATION 3

-CHLOROFORM

BENZENE

i NON-HYDROCARBONS

fTOLUENE

EQUIUBRATION 2 EQUILIBRATON 4

123
It has been postulated that up to 90 x 10^ (5,500 m); the average depth of the ocean

tons of volatile petroleum hydrocarbons are is 8,600 feet (2,600 m). Thus, the volume

discharged to the atmosphere each year and ratio of effective atmosphere to water is an estimated 10% returned to the oceans approximately 2:1.

through rain out [9].

The last line of Table I presents the

The analytical method described above partitioning of the various hydrocarbons

makes it possible to predict the distribu- h5tween the atmosphere and natural waters

tion of hydrocarbons between the atmosphere, assuming equilibrium. Even at equilibrium,

fresh water, and sea water [10]. To evalu- almost all of the low-molecular-weight

ate what may happen to volatile hydrocarbons hydrocarbons (up to 12 carbon atoms in a dischargeJ onto water and to those hydro- molecule) would be in the atmosphere. The

carbons which are released to the atmos- exception is aromatic hydrocarbons, which

phere, equilibrium distributions of repre- are approximately equally distributed. How- sentative hydrocarbons in fresh and sea ever, equilibrium conditions are unlikely

water for various volume ratios of gas to because of the long times for their mixing

water were calculated and are shown in into deeper waters; the effective atmosTable I. The partitioning has been sub- phere-to-water ratio must be much greater

stantiated experimentally for a number of than 2:1. Thus, practically all the lowerthe hydrocarbons [11]. molecular-weight hydrocarbons will be found

in the atmosphere.

The data in Table I demonstrate that

as the gas-water volume ratio increases. Only a few measurements of lowthe percentage of total hydrocarbon in- molecular-weight hydrocarbons have been creases in the gas phase. The various made in the atmosphere and in ocean waters

classes of hydrocarbons partition accord- in remote areas (see [10] for references),

ing to their solubilities in water relative

to their vapor pressures. Thus, partition- Methane is the single predominant

ing into the gas phase decreases in the hydrocarbon in the atmosphere and natural

order alkanes, olefins, cycl oal kanes , and waters. There is substantial agreement on aromatics. Within a given hydrocarbon the concentration of methane in the atmosclass type and for a given gas-water volume phere and worldwide it appears to range

ratio, hydrocarbons partition more into the between 1.2 and 1.5 ppm. Several investigas phase as molecular weights of the hydro- gators have found methane in open ocean or carbons increase. other remote waters to be in approximate

equilibrium with that of the atmosphere

One-half of the earth's atmosphere (the western Atlantic [12], the Atlantic

exists between its surface and 18,000 feet Ocean west of Ireland [13], and the Cook

Inlet [6]).

Table I. Partitioning of selected hydrocarbons between different volumes of

gas and waters (percentage in gas phase).

HYDROCARBONS

Normal Al kanes Al kenes Cycl oal kanes Aromati cs

Gas-Hater

Rati 0 Methane Ethane Pentane Decane Propene 1- Hexene 1-Octene

Cyclopentane

MethylCyclo- Hexane Benzene Tol uene

Ethyl- Benzene

Fresh Hater

1:10 72 9 67 0 83 7 98 2 46 2 62 0 78 9 27 4 60 8 2 2 2 6 3.3

1 :5 84 3 80 3 91 1 99 1 63 2 76 6 88 2 43 0 75 6 4 3 5 1 6.3

1 : 1 96 4 95 3 98 1 99 8 89 6 94 2 97 4 79 0 93 9 18 5 21 2 25.3

5:1 99 3 99 0 99 6 100 97 7 98 8 99 5 95 0 98 7 53 2 57 4 62.8

10:1 99 6 99 5 99 8 100 98 9 99 4 99 7 97 4 99 4 69 4 72 9 77.2

Sea Water

1:10 79 4 74 3 88 0 98 7 55 1 70 0 84 2 35 0 68 8 3 1 3 7 4.6

1 :5 88 4 85 3 93 5 99 4 71 1 82 3 91 4 51 9 81 5 6 1 7 1 8.9

1 :97 5 96 7 98 7 99 9 92 5 95 9 98 2 84 4 95 7 24 5 27 8 32.7

5:1 99 4 99 3 99 7 100 98 4 99 1 99 6 96 4 99 1 61 8 65 8 70.8

10:1 99 7 99 7 99 9 100 99 2 99 6 99 8 98 2 99 5 76 4 79 4 82.9

2:1 98 7 98 3 99 3 99 9 96 1 97 9 99 1 91 5 97 8 39 3 43 5 49.3

124
other low-molecular-weight hydrocarbons have not been found in the atmosphere and open sea water in expected con- centrations if a buildup was occurring with

time. This suggests that these hydrocarbons discharged to the environment undergo

chemical or biological alterations. Photooxidation probably is the principal destructive mechanism for hydrocarbons in the

atmosphere, and bi odegradati on for hydrocarbons in aqueous media.

Extensive measurements with a highly

sensitive marine seep detector which measures C] through C4 hydrocarbons in the sub

parts per trillion range has failed to show

a buildup of these hydrocarbons in sea water [14].

Thus, the evidence suggests no buildup

of Ci-Ci2 hydrocarbons in either the atmosphere or natural waters.

REFERENCES

[1] McAuliffe, C. D. , GC Determination of

Solutes by Multiple Phase Eguilibration, Chem. Tech. 1, 46-51 (1971).

[2] Wasik, S. P. and Brown, R. L., Determination of Hydrocarbon Solubility in

Sea Water and the Analysis of Hydrocarbons in Water-extracts, Proceedings

of Joint Conference on Prevention and

Control of Oil Spills, March 13-15,

1973, Washington, D.C., Amer. Pet. Inst., Washington, 223-227 (1973).

[3] McAuliffe, C. D., Solubility in Water

of Paraffin, Cycl oparaf f i n , Olefin,

Acetylene, Cycloolefin, and Aromatic

Hydrocarbons, Jour. Phys . Chem. 10 , 1267-1275 (1966T:

[4] McAuliffe, C. D. , Determination of

Dissolved Hydrocarbons in Subsurface

Brines, Chem. Geol

4, 225-233 (1969).

[5] Novik, J., Zlutickjr, J., Kubelka, V.,

and Mostecky, J., Analysis of Organic

Constituents Present in Drinking

Water, Jour. Chrom. 76, 45-50 (1973).

[6] Kinney, P. J., Schell, D. M. and

Button, D. K., Analytical Detection

of Hydrocarbon Pollution in Alaska's

Cook Inlet, Institute of Marine

Science Report R-69-16, Univ. of

Alaska, College, Alaska (1970).

[7] McAuliffe, C. D. et al , The Chevron

Main Pass Block 41 Oil Spi 1 1 --Chemi cal

and Biological Investigations, (report

in preparation).

[8] Kreider, R. E., Identification of Oil

Leaks and Spills, Proceedings of

Joint Conference on the Prevention

and Control of Oil Spills, June 15-17,

1971, Washington, D.C., Amer. Pet. Inst., Washington, 119-124 (1971).

[9] SCEP, Study of Critical Environmental

Problems, Man's Impact on the Global

Environment, MIT Press, Cambridge

(1970) 319 pp.

[10] McAuliffe, C. D., Partitioning of

Hydrocarbons Between the Atmosphere

and Natural Waters, Background Papers

for a Workshop on Inputs, Fates and

Effects of Petroleum in the Marine

Environment , Vol. I, p. 280-290,

National Academy of Sciences, Washington (1973).

[11] McAuliffe, C. D., Solubility in Water

of Normal Cg and Cio Alkane Hydrocarbons, Science 158 , 478-479 (1969).

[12] Swinnerton, J. W., Linnenbom, V. J. and Cheek, C. H., Distribution of

Methane and Carbon Monoxide Between

the Atmosphere and Natural Waters,

Environ. Sci . and Tech. 3, 836-838

(1969).

[13] Swinnerton, J. W. and Linnenbom,

V. J., Gaseous Hydrocarbons in Sea

Water: Determination, Science 156 , 1119-1120 (1967).

[14] Jeffery, D.A. and Zarrella, W. M.,

Geochemical Prospecting at Sea, Bull. Amer. Assoc. Pet. Geol. 54, 853-854

Key Words: Distribution coefficient.

Environmental surveys. Equilibration, Gas chromatography. Hydrocarbons in atmosphere.

Hydrocarbon types. Hydrocarbons in water.

Partitioning of hydrocarbons.

125

NBS Spec. Publ. A09, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthers- burg, Maryland, May 13-17, 1974 (Issued December 1974).

SUSPENSIONS OF CRUDE OILS IN SEA WATER: RAPID METHODS OF CHARACTERIZING

LIGHT HYDROCARBON SOLUTES

l

Roger M. Bean

Ecosystems Department

Battel le, Pacific Northwest Laboratories

Richland. WA 99352

Analytical methods for determining volatile

hydrocarbons dissolved in aqueous media using

gas chromatography have been summarized by

McAuliffe [IJ. In addition to direct injection

techniques , these Include concentration by solvent extraction and gas equilibration. Methods

using gas equilibration of water samples have provided analytical sensitivity well under one part-per-billion for individual hydrocarbon

compounds [2]. A similar approach by Brooks, et al. [3] permitted determination of methane

concentrations in the Gulf of Mexico in the parts-per-trillion range. However, differences

1n hydrocarbon vapor pressure require repeated

gas equilibration for quantitation of the full range of soluble hydrocarbon compounds. Com- bination gas chromatographic and mass spectrometric methodologies were utilized by Boylan

and Tripp [4] to identify components of crude

oils and kerosine extracted into sea water.

In addition to methods involving gas chromatography, spectroscopic methods for the determination of hydrocarbons in sea water have

been reported in the recent literature. Brown,

et al. [5] have reported the use of infrared

spectroscopy to determine the extractable organic content of deep sea water. Fluorescence

spectroscopy has been used by Levy [6] to measure trace quantities of oil in marine waters. These optical methods, however, relate to the analysis of heavy hydrocarbon residues.

The purpose of this study was to develop

rapid means for analysis dissolved light

hydrocarbons with respecc to hydrocarbon type,

which would be suitaBle for characterization

of bioassay treatment media and oil/water discharges of a similar nature. To accomplish

this, it was also necessary to develop methods

for sampling at locations remote from analytical instrumentation, and for correlation of

hydrocarbon composition with simple spectrophotometric methodology. Accordingly, a rapid gas chromatographic method was developed to determine the light hydrocarbon composition of

oil/seawater systems. A filtration technique

was investigated as a means of removing interfering insoluble hydrocarbons from water prior

to analysis. The results of the gas chromatographic analyses were then compared with

Infrared absorbance data to determine the

^This work was supported by Battel le. Pacific

Northwest Laboratories through an Internal research and development grant.

potential of the IR technique for routine

monitoring measurements.

Experimental

Crude oils utilized for these studies were

South Louisiana crude, a well -characterized

American Petroleum Institute reference oil [7], and Prudhoe Bay crude, which has been studied in some detail by the U. S. Bureau of Mines [8].

Preparation of oil/water mixtures for study

followed three general procedures. In the first

procedure, a crude oil/seawater mixture (1:45) was shaken vigorously with sea water in a sepa- ratory funnel for five min, allowed to stand for

30 min and filtered with pressure through 0.45 v filter previously solvent extracted to remove interfering organic material. In the second

procedure, oil/water mixtures in the same volume

ratios as above, were agitated in Teflon-sealed

bottles with a mechanical shaker for a minimum of

thirty min, the phases allowed to separate at seawater temperature (9*'C) overnight, and the aqueous layer drawn off using a glass syphon. The

mixtures prepared by the above two procedures were

diluted with additional sea water to obtain con- centration ranges appropriate for study.

The third type of oil /water mixture was

prepared by metering the crude oil into a tank containing flowing sea water while vigorously

stirring with an electrically-driven impeller.

The bulk of the insoluble oil was allowed to over- flow a standpipe, and the mixture of interest,

containing soluble hydrocarbon and small oil droplets, was drawn off from below. A range of

concentrations of oil in water was prepared by

appropriate adjustments of oil and water Inflow,

and of mixer stirring speed.

Water samples were extracted with 20 ml of

carbon tetrachloride and the extracts drawn off

into vials fitted with Teflon-lined caps. Re- peated analysis of selected samples showed no detectable change in concentration of hydrocarbon

components over a period of several months. In- frared spectra from 3200 cm"^ to 2750 cm'^ were

obtained on the extracts in 10 mm quartz cells.

Gas chromatography was performed on aliquots

of the solvent extracts. Two ml of solvent ex- tract was pipetted into a small glass-stoppered

vial. To this was added 5.0 yl of a solution of

indene (5 ul/ml) in carbon tetrachloride as an internal standard. 3.0 yl was injected onto a 17' X 1/8" stainless steel column packed with 4% carbowax 20M TPA on 100-120 mesh chromosorb W. Instrument conditions were: air, 300 ml/min;

hydr^^en, 2K) ml/min; nitrogen carrier, 40 ml/min

at a column^ head pressure of 40 psi. The column

was temperature programmed at 5''C/m1n from an initial temperature of SO'C. Instrument detection sensitivity was 4 x lO-^^ amps.

Results and Discussion

A gas chromatogram obtained from the extract

of a filtered suspension of Prudhoe Bay crude oil

in sea water is shown in Figure 1. Under the conditions used, the benzene peak appears high

127
Figure 1

8 12

TIME (MINUTES)

Gas Chromatogram of CCl^ Extract of Bioassay Water

on the solvent tail and is normally off-scale.

However, satisfactory integration of all hydrocarbon components could be accomplished with an AutolabR computing integrator, permitting an unattended analysis. Compounds emerging after o-xylene were not separately identified and are designated as "C9+ monoaromatics". Saturated

hydrocarbons with boiling points of 100°C or

less emerge before the solvent peak. An esti- mate of these "-100°C sats" was made using the response of n-heptane as a reference.

The appearance of the carbon tetrachloride

peak at a retention time intermediate to those

of the light saturates and the aromatic compounds permitted a rapid estimation of hydrocarbons by compound type. Total time required for

the chromatogram, including instrument recycle,

was 35 min. Limits of detection of components

in water samples of one-half liter were approximately 0.01 mg/1 with the exception of benzene.

The position of the benzene peak on the solvent

tail precluded detection at levels below about

0.1 mg/1.

The gas chromatographic methodology used

for this study was found to be applicable to unfiltered water samples containing on the order of 1 mg/1 dissolved hydrocarbons, and not containing appreciable (> 30 mg/1) quantities

of insoluble (unfilterable) oil. The presence

of more than this amount of insoluble oil in the sample seriously interfered with the analysis

by contributing nonaromatic peaks in the aromatic

region of the chromatogram, and by interfering

with the internal standard peak. Pressure

filtration of the water sample through 0.45 u filters effectively removed these sources of

error; however, the use of the filtration

technique introduced the possibility of low reported values for soluble hydrocarbons because

of mechanical and evaporative losses.

The extent of soluble hydrocarbon losses brought about by pressure filtration was investigated using both infrared and gas chromatographic

methods. In the first study, one-half of a filtered aqueous extract of Prudhoe Bay crude oil was filtered again, and the two halves extracted

with carbon tetrachloride. Losses of hydrocarbon

were estimated by comparing the infrared absorbances. The results of three such experiments

indicated that at least 85% of dissolved hydro- carbons could be recovered using the filtration

technique. Comparative gas chromatographic

analyses of filtered and unfiltered Prudhoe Bay

crude-seawater mixtures generated using the "mixer/settler" apparatus are shown in Table I. The component analyses of unfiltered and filtered

Table I. Comparison of Gas, Chromatographic Analyses of Filtered and Unfiltered Samples from "Mixer-Settler" Discharges (cciit Extracts)

COMPONENT CONCENTRATION (mg/1)

COMPONENT

24.9 mg/1 TOTAL OIL 12.9 mg/1 TOTAL OIL 6.6 mg/1 TOTAL OIL UNFILTERED FILTERED UNFILTERED FILTERED UNFILTERED FILTERED

-100°C SATS 2.90 1.79 0.92 0.61 0.35 0.22

BENZENE 0.20 0.15

TOLUENE 0.69 0.63 0.34 0.36 0.14 0.14

ETHYL BENZENE 0.11 0.08 0.04 0.04 0.03 0.01

M, P-XYLENES 0.45 0.40 0.26 0.20 0.11 0.08

O-XYLENE 0.15 0.14 0.09 0.07 0.04 0.03

C9+ MONOAROMATICS 0.75 0.24 0.40 0.13 0.09 0.03

128
extracts again demonstrate good recovery of

hydrocarbon components with the exception of the C9+ monoaromatics. The much higher values re- ported for the C9+ monoaromatics are a result of

interference from insoluble (filterable) non- aromatic components. Losses of saturates upon filtration are somewhat higher than those for aromatic compounds, a reflection of their higher

vapor pressure.

Extraction of oil/seawater mixtures with

carbon tetrachloride afforded an opportunity to investigate quantitative relationships between

hydrocarbon composition as determined by gas chromatography and the corresponding infrared

spectra. Figure 2 shows examples of spectra for whole Prudhoe Bay crude oil in carbon tetrachloride, and for extracts of unfiltered and filtered seawater extracts of the crude.

WHOLE CRUDE OIL J I IFILTERED EXTRACT J I \

2930 cm'l

UNFILTERED EXTRACT J L

3200 3000 2S00 3200 3000 2800 3200 3000 2800 WAVENUMBER (cm-l|

Figure 2. Infrared spectra of Prudhoe Bay crude, and filtered and unfiltered seawater

extracts of Prudhoe Bay crude

The spectra obtained from the seawater extracts exhibit sharp bands at 3040, 3070, and 3090 cm-^ which do not appear in solutions of the whole

crude. These bands characteristic of alkyl

substitution on aromatic rings [9] have been used

by Frankenfeld [10] to qualitatively estimate

losses of light aromatics from crude oils

during the process of weathering. The enhance- ment of absorption in this region occurring in aqueous extracts of oil is a result of the greater solubility of aromatic hydrocarbons than saturate molecules having equivalent mole volumes [11]. The reduction in absorbance at 2930 cm'' of the filtered sample relative to unfiltered is interpreted to be a consequence

of evaporation losses, and removal of higher

molecular weight saturate hydrocarbons, which

are "accomodated" in the sea water [12] rather

than in true solution.

Figure 3 shows the relationship established

between the concentration of total monocyclic

aromatics as determined by gas chromatography,

and the absorbance at 3040 cm"^ per liter of water extracted. A similar comparison between

o

>-

So

- A

- O

—'

1

1 1

'

1

UNFILTERED AQUEOUS EXTRACT

OF PRUDHOE BAY CRUDE O FILTERED AQUEOUS EXTRACT OF PBC

UNFILTERED AQUEOUS EXTRACT OFS. LOUISIANA CRUDE

FILTERED AQUEOUS EXTRACT OFSLaC

o o'

SLOPE = 26.06 +0.39

2^

CORRELATION COEFFICIENT OF X WITH Y: 0.993 I I I < \ I I 1 1

0.1 0.2 0.3 0.4

Figure 3.

X: ABSORBANCE AT 3040 cittI OF CCI4 EXTRACTS

PER LITER OF WATER EXTRACTED

Correlation of aromatics concentration

in seawater extracts with infrared

absorbance at 3040 cm"^

saturate content and absorbance per liter at 2930 cm"^ is shown in Figure 4. The high values of the correlation coefficients obtained is good

evidence that quantitative estimates of concen- trations of hydrocarbon types can be made by

referring to the infrared absorbances of carbon tetrachloride extracts at the appropriate

wavelengths.

It is important to note that application of Infrared absorbance measurements to compoundtype analysis of hydrocarbon solutes is limited

to those mixtures containing negligible quantities

of insoluble oil, since absorbance from the whole

oil masks the contribution to the spectra of the light hydrocarbon components. The filtration

technique which was applied to gas chromatographic

analysis was, therefore, investigated as a means of removing Insoluble oil droplets prior to determination of compound-type distribution by

infrared spectrophotometric means. Thus,

generated by the "mixer-settler" apparatus,

mixtures containing up to 70 mg/1 of suspended

petroleum, were filtered, and the infrared

absorbance of solvent extracts compared with the determined concentrations of hydrocarbon types

as in Figures 3 and 4. Again, linear relationships were established between infrared absor- bance and concentration of hydrocarbon type,

although in the case of the saturates, the determined slope (6.01 +0.32) was significantly

different from that obtained previously

(3.21 + 0.13).

129
"8

zo

o

UNFILTERED EXTRACT OF PRUDHOE BAY CRUDE

I- O FILTERED EXTRACT OF PBC A UNFILIERED AQUEOUS

EXTRACT OF SOUTH

LOUISIANA

FILTERED AQUEOUS

EXTRACT OF SLaC

SLOPE = 3.21 ±0.B

CORRELATION COEFFICIENT

OF X WITH Y: 0.960

3.0

X: ABSORBANCE AT 2930 cm'' OF CCI4 EXTRACTS

PER LITER OF WATER EXTRACltD

Figure 4. Correlation of saturates (4 lOCC)

in seawater extracts with infrared

absorbance at 2930 cm-^

Infrared absorbance measurements on carbon tetrachloride extracts of filtered oil /water

mixtures are presently being used to monitor

concentrations of light hydrocarbon solutes in toxicity experiments being conducted in these

laboratories. As evidenced from the above

studies, however, the practical utility of this methodology for routine monitoring is contingent

upon first establishing independent data on hydrocarbon composition by other means. The

gas chromatographic method developed for these

studies appears well suited for this purpose be- cause of the relatively short time required for the analyses.

References : [1] McAuliffe, C, Chem. Geol . . 4, pp 225-233

(1969). ~

[2] McAuliffe, C, Chem. Tech .. 1, pp 46-51 (1971). -

[3] Brooks, J. M., Fredricks, A. D., Sackett,

W. M., Swinnerton, J. W., Environ. Sci . Techno! . . 7, pp 639-642 (1973).

[4] Boylan, D. B., Tripp, B. W. , Nature . 230,

pp 44.47 (1971).

[5] Brown, R. A., Searl , T. D., Elliott, J. J., Phillips, B. 6,, Brandon, D, E., Monaghan,

P. H., 1973 Proc. Conf. on Prevention and

Control of Oil Spills, pp 505-519. March 13-15, 1973.

[6] Levy, E. M., Water Res .. 5, pp 723-733 (1971).

[7] Vaughan, B. E., Ed., "Effects of Oil and Chemically Dispersed Oil on Selected Marine

Biota", Battel le. Pacific Northwest

Laboratories, Richland, WA (API Publication

No. 4191), (1973),

[8] Thompson, C. J., Coleman, H. J., Dooley, J. E. Hirsch, D. E., Oil Gas J .. 69 (43) pp 112-120

(1971).

[9] Alpert, N. L., Keiser, W. E., Scymanski, H.A., "Theory and Practice of Infrared Spectroscopy"

p 207, Plenum Press, New York, NY, (1970).

[10] Frankenfeld, J. W., 1973 Proc. Conf. on Prevention and Control of Oil Spills,

pp 485-495, March 13-15, 1973, American

Petroleum Institute, Washington, D.C. (1973).

[11] McAuliffe, C, J. Phys. Chem .. 70, pp 1267-

1275 (1966). ~

[12] Peake, E., Hodgson, G. W., J. Am. Oil Chem . Soc . 43, pp 215-222 (1966):

Key Words: Crude oil suspensions. Gas chroma- tography. Filtration of insoluble oil. Hydrocarbon

solutions in water. Hydrocarbon type determination

by IR. Infrared spectrophotometry.

130
BBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum)

,

Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland. Hay 13-17, 1974 (Issued December 1974).

MEASUREMENT AND CHARACTERIZATION OF NONVOLATILE HYDROCARBONS IN OCEAN WATER

R. A. Brown, J. J. Elliott and T. D. Searl

Esso Research and Engineering Company

Linden, New Jersey 07036 U.S.A. A method Is described for the measurement and characterization of nonvolatile hydrocarbons (Cj^^ and heavier) In ocean water. The method was applied to total dispersed hydrocarbons which gen- erally occur In the concentration range, 0-20 ppb

(wt.).

Description of Method

The procedure involves extraction of hydrocarbons from ocean water followed by an infrared measurement of the extracted organics. Following this, the sample is placed on a silica gel column and hydrocarbons are eluted as a fractlon(s) which is examined by infrared and ultraviolet absorption

spectrophotometers, gas chromatograph and mass

spectrometer. Individual steps of the method are shown in Figure 1. In essence, the procedure is based upon extending techniques for handling milligrams to microgram quantities of hydrocarbon. A

parallel effort was required to minimize and control contamination so that it could be monitored by

judicious use of sample blanks.

Obtain 3 to 20 Liter Sample

J Extract Sample with

25 to 125 ml Carbon Tetrachloride

I IR Measurement of Extractable Organics

Reduce Sample to 2 ml by

Controlled Evaporation

of Carbon Tetrachloride,

Add 0.1 nd of n-pentane

Silica Gel Column Separation

i

Carbon Tetrachloride + n-Pentane (1%) Saturate Hydrocarbons

Chloroform + Benzene (1%) Aromatic Hydrocarbons

Evaporate Chloroform, n-Pentane

and Benzene, Replacing with

Carbon Tetrachloride

IR Measurement of Total Hydrocarbons

Evaporate Carbon Tetrachloride,

Replacing with Isooctane to Final Volume '\4 ml

UV Analysis

Evaporate Isooctane to '^'0.5 ml _jGC, MS Analysis

Figure 1. Analytical Method for Nonvolatile Hydrocarbons in Ocean Water.

131
Practice of the Method Typical Results

Based on considerable experience, this method

is now used to routinely analyze large numbers of ocean water samples. The method is modular in nature and based upon need and/or interest a number of options are available:

• An extractable organic value (hydrocarbons plus other lipids) can be obtained by carrying out

the first two steps of the method - extraction

and infrared measurement.

• Total hydrocarbons per se or subclassified as saturates and aromatics can be measured by

using extraction, silica gel separation and an infrared measurement.

• Hydrocarbon composition can be based on one or all of the techniques - UV spectrophotometry,

gas chromatography and mass spectrometry.

Samples to be analyzed are collected from moving tankers or from oceanographic research vessels . From three to nine liter samples of ocean

water are extracted with CCI4 as samples are taken from aboard a tanker . The extract is then sent to the laboratory for final analysis. In order to achieve greater sensitivity, approximately twenty

liter samples are usually collected off research

vessels. At the time of collection, 25 ml CCI4

is added to preserve the sample until it can be

analyzed.

In measuring and characterizing hydrocarbons,

it is the practice to simultaneously handle four unknown samples and a blank. This can be con- veniently done by carrying out evaporations on a multi port steam bath and the hydrocarbon separations on a manifold supporting the operation of five silica gel columns. Improved efficiency can

also be achieved by queuing up samples for IR, UV, GC and MS measurements . By adhering to this mode

of operation, it is possible for a technician to analyze one or more samples a day depending upon

the amount of information desired. Extractable

organic measurements, for example, may be done at the rate of twelve or more per day.

Considerable work was done to evaluate the efficacy of the method. Information on the key

items of interest are listed in Table I.

The initial steps of the method include CCI4 extraction of the ocean water followed by an in- frared measurement of the organics in the extract. At the level of concentration normally encountered

(ppb), these organics include hydrocarbons, esters

and acids. Thus, this measurement provides what

is defined as an extractable organic value. This

parameter is quite useful in base line studies as it represents a maximum hydrocarbon concentration

and since it is easily measured it is possible to obtain an overall picture without necessarily

determining the hydrocarbon content of every sample

The magnitude of extractable organic and total hydrocarbon measurements is Illustrated by

the data in Table II which summarizes results for samples collected along three different tanker

routes. These samples were taken from near the

top surface of the water using a stainless steel bucket to scoop up the water. Median concentrations of 18-33 ppb and 3-7 ppb were observed for extractable organics and hydrocarbons, respectively. For these median values, hydrocarbons were

found to represent from 13-21% of the extractable

organics

Table II. Extractable Organics and Hydrocarbons for Three Tanker Routes

Tanker Route

Extractable Organics

Range , ppb

Median, ppb

Hydrocarbons

Range , ppb

Median , ppb

Median Hydrocarbons/

Median Extractable

Organics

10-63

23

2-21

3

137o

9-67

33

1-22

7

21%

4-442

18

1-194

3.5

20%

Tanker Route 1 - Gulf of Mexico/New York [1]

Tanker Route 2 - Caribbean/New York [1]. Tanker Route 3 - Intra Mediterranean (La Spezia,

Italy/Brega, Libya) [2].

Item

Table I. Evaluation of Method

Observation

IR Calibration

at 2930 cm-1

CCl^ Extraction

Silica Gel

Separation

Precision

Sensitivity

Average Coefficient =2.19 %l%

cm, variation, 2a = 28 relative

percent. Based on 33 different

crude oils. 80-111% recovery for known

blends of hydrocarbons in ocean

water. 90-100% recovery for known

blends of hydrocarbons in CCI4. +10 relative percent for '\'40 pg

of hydrocarbons

6 pg of hydrocarbon.

Compositional information is derived from examination of silica gel fraction(s) by UV, GC and mass spectrometer. UV spectra provide insight

as to the approximate level of dicyclic and higher

aromatic hydrocarbons based on absorption bands

at or near 228 nm and 255 nm. Another value of the UV is that zero absorption is a reliable indication for absence of aromatics.

Figure 2 presents some gas chromatograms of hydrocarbons as found in some South Atlantic locations that were sampled for us by the GEOSECS

Project. The observed carbon number range of C]^4- C35 is typical. Hydrocarbon type analyses by the mass spectrometer invariably show that saturate hydrocarbons are predominant and consist of paraffins and 1- to 6-ring cycloparaf f ins . Aromatic

hydrocarbons are usually found and consist of

132
I I I I I I I I I I I I I I I I I I I I

SURt'ACE SAMPLE

STATION 89 LAT. 60° 00\S LONG. 0° 3'W

I I I I

1 I I r A,

SURFACE SAMPLE

STATION 91 LAT.49°3S'S LONG. 11°33'E

I I I I I I I I I I I I I I I I I I I I I I I

C15 C14

I I I I |C24| I I I I I I i I I I I

SURFACE SAMPLE

STATION 93 LAT. 41°47'S LONG. 18°27'E

I I I I I I I I I I I I I I I I I I I I I I I I I 48 47 i6 45 44 43 42 41 40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 2) 20 19 13 17 16 15 14 13 12 RETENTION TIME (min.)

Figure 2. Gas Chromatograms of GEOSECS Samples

1- to 3-ring compounds. Of the samples from the tanker routes listed in Table II that were

analyzed for compound types, aromatlcs were found

to comprise from 3-67% of the total hydrocarbons.

The median aromatic con'^e.ntration was 16 percent.

References:

[2] Monaghan, P. H. , Seelinger, J. H. and Brown,

R. A. , The Persistent Hydrocarbon Content of the Sea Along Certain Tanker Routes - A

Preliminary Report . American Petroleum

Institute Report of the 18th Annual Tanker

Conference, May 7-9, 1973, Hilton Head

Island, South Carolina (1973) 298 pp.

[1] Brown, R. A., Searl, T. D., Elliott, J. J., Phillips, B. G., Brandon, D. E. and Monaghan, P. H. , Distribution of Heavy

Hydrocarbons in Some Atlantic Ocean Waters , Conference on Prevention and Control of Oil

Spills, March 13-15, 1973, Washington, D.C. Library of Congress Catalog No. 74-124324

(1973) 834 pp.

Key Words: Chromatography, Hydrocarbons Ocean

Water; Hydrocarbons Along Tanker Routes; Lipids

Along Tanker Routes; Hydrocarbons Ocean Water; Lipids Ocean Water; Measurement Hydrocarbons,

Lipids Ocean Water.

133

HBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposliim and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

IDENTIFICM'Kaj, ESTIMATICM AND

MOJITORING OF PETRDIEUM IN MARINE WATERS BY LUMINESCEN(2: METHODS

A. W. Homig

Baird-Atomic, Inc. Bedford, MA 01730 U.S. A,

The use of UV-excitation spectroflijorimetiy as described by Levy (1) is reconwended by lOCAiMO

for detecting and measuring dissolved and finely

dispersed polynuclear aromatic hydroc.^.-bons in sea water. Levy found that the fluor scence method of analysis is more sensitive and less subject to interference than the siitple absorbance method and is therefore superior, especially

when the concentrations of residual oils in the sea water are less than 10 ppb. In the remainder

of this talk I would like to e:5)and on the potential of luminescence metiiods, with specific exam^

pies.

Luminescence offers a specific and sensitive

method for the study of oil in water. The three

wavelength parameters of excitation, fluorescence

and phosphorescence usually provide sufficient

specificity for oil classification. Since the luminescence quantum efficiency of aromatics

in oils is usually high, sensitivity is also

high. Detection may be remote or in the laboratory on grab samples. The latter allow concen- tration by extraction and low-tenperature anal'.

sis. Interferents may be humic materials

((Selbstoffe) or fish oils. The selectivity of

the method usually allows discrimination against

such interferents.

Identification is best accoitplished by

studying the Total Luminescence Spectra (TLS) of

dilute oil sanples. This allows correlation

between known and unknown sairples, and typing of

oils. Low tenperature analysis further increases

specificity by increased structure and the ap- pearance of phosphorescence. Estimation of oil

concentration requires the availaoility of a known sample, or calibration with another refer- ence n^thod, e.g., infrared analysis.

Surface films, and to some extent dissolved

and emulsified oils, may be monitored remotely or via continuous flow systems. All forms of oils,

including that adsorbed onto particulates, may be

studied by extraction of grab sanples into a

selected organic solvent.

In the following sections we describe the

origin of molecular luminescence and the luminescence characteristics of some petroleum oils.

Monitoring methods appropriate to the physical

forms of oils present in marine waters are also

discussed.

For all practical purposes, molecular lumin- escence (light emission) occurs only for aromatic

molecules, i.e., those having the benzenoid ring

system. Exanples are benzene, naphthalene, biphenyl, anthracene, and their derivatives.

The physical processes involved in lumines- cence are shewn diagramatically in figure 1. Emission occurs after light of an ^propriate

wavelength is absorbed by the molecule. The

energy absorbed may be re-emitted either as fluorescence or as phosphorescence. Fluorescence is defined as emission which occurs fran an excited singlet electronic state (usually

the lowest) ; the lifetime of this emission is very short, usually on the order of nanoseconds.

Fijosjfiiorescence is defined as emission which

occurs from a triplet electronic state (usually the lowest) . This emission is of longer wavelength than the fluorescence and is of much

longer lifetime; usually the range of 10"^ to

10 seconds. Triplet states significantly

populated only by absorption into singlet

states, vitierei:pon the molecule undergoes a non- radiative process called intersystem crossing.

The longer phosphorescence lifetime makes it more susceptible to quenching so that phosphorescence is ordinarily observed only at lew

tenperatures (<100°K)

.

The rocm tenperature fluorescence properties

of oils have been studied by many workers (2-9),

and the author and co-workers (10, 11) have

shewn that luminescence analysis at low tatperature frequently results in improved sensitivity

and selectivity. Crude oils are e:^cted to emit fran the near ultraviolet (benzene derivatives) to the deep red (large polynuclear aromatics) . Refined oils are expected to emit over a narrower spectral range. Light grades

are expected to contain benzene and naphthalene

derivatives, v*iich fluoresce in the 300-400 nano- meter (nm) region. Heavy fractions contain

polynuclear aromatics v*iich would emit at still

longer wavelengths. The wavelength of maximum

emission will be determined by the relative concentrations, fluorescence quantum yields, and

interactions among the Quitting ccnponents.

These expectations are verified in a model oil

study undertaken by Baird-Atemic for EPA (12)

.

Figure 2, taken from this study, shews the

principal emissions of a naphthenic crude and

four oils refined from this crude. These measurements were made front surface on lOu

films of undiluted oil using a Baird-Atemic

SF-lOO Fluorispec spectrofluorimeter. (Spectral

intensities obtained with this instrument are not corrected for instrument response.) The

lighter oils have their peak emissions near

350 nm, whereas the heavier oils have peak

emissions in the 400-500 nm region. The parent

crude, which contains all emitting moieties,

peaks near 450 nm, intermediate between #4 and

#6. The corresponding excitation spectra for

these oils (which are related to the absorption

spectra) are given in figure 3. These may also

be useful for identification or classification.

Spectra of oil films and emulsified oil are expected to be similar if film thickness and par^

tide diameter are similar. Figure 4 shews the

135
principal fluorescence emissions of 11 oils

emulsified in deionized water at nominal concen- trations of 50 ppm. The mean droplet size for these oils is probably in the 5-lOu range. Note

in particular that the spectra of #4 oils from

two different sources are quite different.

Dissolved oil in marine waters may also be

detectable by fluorescence. Marine water saitples

collected near Gloucester, Massachusetts, were

doped with both a #2 fuel oil and a crude. After

stirring slavly for a day, sanples of the water

were ren&ved and transferred to a cuvette for

flxoorescence analysis. Figures 5 and 6 cctnpare the fluorescence with that of the same oils

emulsified in deionized water.

The fuel oil peaks shew a small shift to

shorter wavelengths in the dissolved sartple, but

the structure is not greatly changed. This is because the principal fluorescing cctiponents in the pure oil are also those which have the high- est solubility in water. A much greater change occurs for the cruie: The fluorescence of the soluble conponent is at much shorter wavelengths,

and in fact resembles the fluorescence of the #2 fuel. The water-soluble catponents of the crvde

are probably chemically similar to those which

are responsible for the fluorescence of the fuel. In fact, cctrparison with the spectrum of naphthalene (fig. 7) suggests that these coipounds may be naphthalene derivatives.

Oil present at very lew concentrations (sub

ppm) in water or biological materials may have

to be extracted prior to analysis. Levy (1) and

Zitko (13) have described sinple fluorescence

methods for quantitating oils in marine water

and aquatic animals. The use of a solvent

generally shifts the principal emission to shorter wavelength because dilution reduces the probability of energy transfer among cotponents.

Although room tenperature fluorescence analysis is often useful, even more information can

frequently be obtained by observing luminescence

at lew tenperature (typically 77°K, liquid

nitrogen tenperature) . At lew tenperature (LT)

,

spectral bands generally become sharper and

oxygen quenching is reduced, resulting in better

sensitivity and selectivity. Figures 8 and 9 shew the room and lew tenperature emission spec- tra of a crude oil dissolved in methylcyclohexane (MCH) at a concentration of 10 ppn. The

spectra shew a sharp system originating near

370 nm which is probably due to a pyrene derivative. This fluorescence is largely quenched at

KT. The emission peaked near 340 nm at both

rocm and lew tenperature is probably due to naphthalene derivatives, and LT excitation of

the same oil at 380 nm (fig. 10) also shews

an emission resembling anthracene.

The phosphorescence emission from oil com- ponents may be ctoserved at LT, but not at rocm

tenperature under normal circumstances. This

emission has a much longer lifetime than

fluorescence and can be observed free of fluores- cence using a phosphoroscope. Figure 11 shews

the luminescence of 10 ppm of an asphalt in MCH

at 77^ taken with and without a phosphoroscope.

Note that the phosphorescence appears buried in

the long wavelength tail of the fluorescence

trace.

Oil present as a surfac-e film may also be

detected by renote sensing devices. Fantasia and

Ingrao (14) , Kim and Hickman (15) and Horvath et

al (16) describe systems which utilize a nitrogen

laser (337 nm) to excite oil fluorescence. A

renxjte sensing device utilizing a lew pressure mercury lamp has been reported by Gram (17) . A

potential disadvantage of nonochiromatic sources

is that certain oils may not be excited efficiently. This difficiiLty has been overcome in a

device described by Eldering and Webb (18) on- ploying a powerful pulsed xenon source coupled to

a tunable monochrcmator, providing variable wavelength excitation. The detection monochromator is also tunable. Emission spectra excited at various

wavelengths can be stored, corrected and displayed

as contour maps of equal emission intensity. In

this format, which we call Total Luminescence

Spectra (TLS) , changes of oil thickness are readily apparent (figs. 12 and 13)

In the marine environment, several other

naturally occurring materials also shew fluorescence. These include fish oils, algae (chlorophyll) , and Gelbstoffe. The chlorophyll emission

occurs near 670 nm, v^ich is at much longer wavelength than the emission maxima of most petroleum

oils. Fish oils have fluorescence vAiich occurs

in the 350-500 nm region (19) , vdiich is in the fluorescence region of many petroleum oils.

Gelbstoffe are a ccirplex mixture of water

soluble decayed organic material. The intensity

and structure of the fluorescence varies somewhat

with location, but generally peaks in the 400-450 nm region and typical fluorescence signatures

are shown in figure 14 taken from (20)

The sensitivity and specificity (especially at low tenperatxares) of luminescence analysis

of petroleum in sea water suggest practical

methods for identifying, estimating and monitoring. Because of the variation of concentrations of luminescence moieties in different

oils the sinple method of Levy on oil extracts will have to be calibrated for each oil type.

A method based on multiple excitation and emission (i.e., the Total Luminescence Spectrum) may be devised to measure a variety of oils. Oils emulsified in sea water may be monitored

continuously in a flew system. Active remote sensing instrunents, mounted on ships or aircraft, may monitor surface films (and possibly

dissolved and suspended oil) . Lew tenperature

analysis of TLS of oil extracts provides the most information on identity concentration. New instrumentation based on the above is cur- rently under development and should be available

for test in the near future.

The author wishes to acknewledge the assis- tance of Dr. J. T, Brewnrigg, Dr. D. Eastwood,

Dr. B, Dalzell, and Ms. G. Gamick, v*io performed much of the experimental work and aided

in the interpretation of tlie work reported here. The data were drawn in part frem a number of contracts s\;pported by the Environmental Protection

Agency, the Coast Guard, the Navy, and NASA.

136
References

(1) Levy, E.M. , Water Res. 5, 723-733 (.1971).

(2) Parker, C.A. and Barnes, W.M. , Analyst 85, 3-8 (1960).

(3) Riecker, R.E., Bull. Am. Assoc. Petrol. Geologists 46, 60-75 (1962).

(4) MOKay, J.F. and Latham, D.R. , Fluorescence

Spectroscopy in the Characterization of

High-Boiling Petroleum Distillates, Proceedings of the ACS 163rd National Meeting,

Division of Fuel Chemistry, i^ril 9-14, 1972,

Boston, Massachusetts, pp. 63-78.

(5) Drushel, H.V. and Sonmers, A.L. , Anal. Chem.

38, 10-19; 19-28 (1966).

(6) Thruston, A.D. and Knight, R.W. , Environ.

Sci. & Technol. 5, 64-69 (1971).

(7) Snoek, D.I., Bouma, M.J.J. , and Van Barren,

F.W.J., H2O 4, 227-232 (1971).

(8) Coakly, W.J., Carparative Identification of

Oil Spills by Fluorescence Spectroscopy,

Proceedings of the Joint Conference on the

Prevention and Control of Oil Spills, March

13-15, 1973, Washington, D. C. , pp. 215-222.

(9) Jadamec, J.R. , Single Wavelength Fluorescence

Excitation for On-Site Oil Spill Identification, Proceedings of Second Conference on

Environmental Quality Sensors (EPA) , Las Vegas Nevada, Octobex 10-11, 1973) Section

VI, pp. 1-20.

(10) Homig, A.W. and Easto/ood, D. , Development

of a Low Tettperature MolecvLlar Emission

Method for Oils, Interim Progress Report for the Period December 1970-August 1971, Pro- gram No. 16020 GBW, U.S. Environmental Protecti-on Agency, Water Quality Office,

Washington, D. C. (August 1971)

.

(11) Homig, A.W. , Eastwood, D. , and Guilfoyle,

J. , ftolscular Lurrdnescence Studies of

PetroJ.eun:! Oils at 77°K, Presented at the Joint Keating Pacific Conference on Chemstry

and Spectroscopy and tiie Amual Jfeetinq of

the Optical Society of America, Ortober

16-20, 1972, San Francisco, Califcmia.

(12) Homig, A, W. , Model Oil Stmy, Preliininaiy

Report, Contract 68-01-0146, U..S. Snvironitent^ Protection Agency, Water Qv.jality

Office, Washington, D.C. (Itece!±ier 1971).

(13) Zitko, V. . Bull. Environ, Contam. & Toxicol.

5, 559-564 JWflTT'

(14) Fantasia, J.F. and Ingrao, H.C., The Develop- ment of an Ei^rimental Airborne Laser Remote

Sensing System for the Detection and Identification of Oil Spills, Suitmaries of P^ers

of 9th International Syirposium on Remote

Sensing of the Environment, Ann Arbor,

Michigan, April 15-19, 1974, pp. 192-193.

(15) Kim, H. H. and Hickman, G. D. , An Airborne

Laser Fluorosensor for the Detection of

Oil on Water, Proceedings of a Syitposiijn on the use of Lasers for Hydrographic

Studies (NAS>-) , Wallops Island, Virginia,

September 12, 1973, pp. 265-274.

(16) HorvaiJi, R. , I'torgan, W. L. and Stewart,

S.R. , OpticaJ. Renote Sensing of Oil

Slicks: Signature Analysis and Systems

Evaluation, Final Report., Contract DOTCG-92589-A, U.S. Coast Guard, Washington,

D.C. (October 1971).

(17) Gram, H.G. , The Remote Detection and Identification of Surface Oil Spills, Proceedings

of Second Conference on Environmental Quality

Sensors (EPA), Las Vegas, Nevada, October

10-11, 1973, Section TO, pp. 21-33,

(18) Eldering, H.G. and Webb, W.A. , MultiSpectral Remote FluoriiTeter for Detection

of Oil Fj.lms, Suirsnaries of Papers of 9th

Iritemational Symposium on Remote Sensijig

of the Environment, Ann Arbor, Michigan,

April 15-19, 1974, pp. 190-191.

(19) Komig, A.W., Fish Oil Filirs on the Sea

Surface, Final Report, Contract N62 306-69-

0354, U.S. Naval Oceanographic Office,

Washington, D. C. (October- 1970)

.

(20) Homig, A. W. and Ec-3te/ood, D. E., A Study

of ^iarine Luminescence Signatures, Final

Report, Contract NAS 2-6403, NASA, /vties Research Center, SvxiTY'.mle, California

(March 1973)

.

Key Words: Analytical methods; Classification of

oils; Fluorescence of oils; Identification of

oils; Ijcw tertperature lumiaescence? Lumiiiescence of oils; Molecular luminescence; Phosphorescence

of oils? Remote sensing; Total iuininescenoe spectroscopy.

137
WBAIfID ATOMIC

Triplet System

kinglet System

Figure 1. Luminescence Eneorgy level Diagram.

BAIRDAIOMICl Samplas: Ashland A »1 Fuel Oil 300

a n " C»4 " D »6 •

E Crude(Noplithenlc) 396

Slit^ 21/12

Time Consfant 0.1 sec. Temperature Room

Recorder 0.01 Max

Comments: Front Surface O.OImm cell

330

396 400

Gain

100/100

100/960

100/515

100/945

100/963

300 ^"^WAVELENGTH (nano.ne?ert)

Figure 2. Principal Fluorescence Spectra of Thin Films of 4 Fuel Oils and the Parent

Crude.

138
1^

Samples: Ashland

342

352 442

SOO

A »1 Fuel Oil

B »2 "

" Cf4 •' " D '6 "

" E Ciude(Naphthenlc) 445

Slits 21/12 Time Constant 0.1 see. Temperature Room

Recorder 0.01 Max

Comments: Front Surface O.OImm cell

Gain

100/100

100/960

100/515

100/945 100A63

20O lATAVELENGTH (nanometen) 700

Figure 3. Principal Excdtation Spectra of Thin Films of 4 Fuel Oils and the Parent Crude.

400 SOO WAVELENGTH ( nanometers ;

Figiare 4. Principal Fluorescence Spectra of 11 Petroleum Oils Emulsified in Water.

139
140
Sample ; Naphthalene

Concentration : 10 ppm in Meth/lc/clohexane

Slits : 22/22

Time Constant : 0.3 sec. Temperature ; Room

Recorder : 50 mv/cm

200 400 500 vVAVELENGTH ( nanometers )

Figure 7. Excitation and Fluorescence Spectra of NaE>hthalene in Methylcyclohexane , 10 ppm

CONCENTRATION Z"/?-"^

SLITS J'V'/ TIME CONSTANT. 3 GAIN 'joj o H oi/ti'^ TEMPERATURE EXCITATION WAVELENGTH-'»<^

EXCITATION iVAVELENGTH GAIN W<-'

FLUORESCENCE WAVELENGTH

3

SLITS ///J* GAIN H c./^t. / TEMPERATURE 'f^'^

lON/EMlSSION SPEC15*

E qiL (24-10) j inMCH _

at ^004JEwjPER A FlM

^400 500 WAVELENGTH (nanometers)

700

Figure 8. Excitation and Fluorescence Spectra of a Crude Oil (24-10) at Roan Temperature

141
Figure 9. Fluorescence Spectra of a Crude Oil (24-10) at 77°K.

Figure 10. Fluorescence Spectrum of a Crude Oil (24-10) at 770K Excited at 380 nm.

142
oncentraf ton iDppir) Slltj 2^1 »

I Recorder .01/max. ' Jhrte Constont ,3 bain -Fluorescence 3/6

[

i Photphoretcence 30/6

Temperature 77°K j Muorescenf Excitation^ 340nm

Phoiphoreicent Excltatlon^^SOOnm

iRESCENC {/PHOSPHORESSENCE

700 WAVELENGTH (nanometere)

Figure 11. Principal Fluoresoence/Phosphoresoenoe EMssions of an Asphalt at 77°K.

250 MICROMETER FILM OF NUMBER 4 FUEL OIL

(CORRECTED OIL SPECTRUM FROM MAPS)

450

400

O

z

•< 350

O

z

>

<zo

300 --

250 -- u

><

200

BAIRD-ATDMIG

1 ."t

200 250 300 350 400 450 500 550 EMISSION WAVELENGTH (NANOMETERS)

Figure 12. MAPS Luminescence Contour for a #4 Fuel Oil, 250 Thick.

143
2000 MICROMETER FILM OF NUMBER 4 FUEL OIL

(CORRECTED OIL SPECTRUM FROM MAPS)

450

o

z

<

o

z

400

350

> 300 <Zo

< 250 u

><

200

BAIRD-ATOMIG

/:-"T;

//;/;;'

:t; fs.ri i

i pit;!: \

200 250 300 350 400 450 500 EMISSION WAVELENGTH (NANOMETERS)

550

Figure 13. MAPS Luminescence Contour for a #4 Fuel Oil, 2000 ym Thick.

400 500 WAVELENGTH (nonometere)

Figure 14. Typical Gelbstoff Fluorescence.

144
NBS Spec. Fubl. 409, Marine Follutlon Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

RECENT DEVELOPMENTS IN THE IDENTIFICATION

OF ASPHALTS AND OTHER PETROLEUM PRODUCTS

F . K . Kawahara

Methods Development and Quality

Assurance Laboratory

National Environmental Research Center

Environmental Protection Agency

Cincinnati, Ohio 45202 U.S.A.

INTRODUCTION

The development and testing of a new concept of oil analysis this past year have made

possible the first successful application of gas chromatography- electron capture (EC) detector to the analysis and identification of heavy lubri- cating oils, residual fuel oils and asphalts.

Asphaltic materials cannot be readily identified

to a source because they are not, by virture of their very high molecular weights and complexity,

usually amenable to analysis by gas chromato- graphy with flame ionization detector. The

limiting difficulty is the inability to vaporize

and to separate the high molecular weight com- ponents in the gas chromatographic column. One successful approach leading to their identification is the use of electron capture detector

gas chromatography to separate the passivelylabeled perfluorobenzyl ether and thioether

derivatives of the weak acids present in discharged heavier petroleum products. Use of

organic minor components, phenols and mercaptans

contained in petroleum, to serve as fingerprints

for identification is relatively new and has not been applied toward the identification of pettoleum products.

The conversion of weak acids to their re- spective novel pentafluorobenzyl derivatives and

the subsequent EC detector gas chromatographic

analysis of certain effluents has provided

technical support in enforcement cases, e.g., tracing of phenols found in the city of

Wheeling drinking water samples. The procedure,

developed at Methods Development and Quality

Assurance Research Laboratories, made possible

the tracking of minute traces of phenols found

in the city water to its source 20 miles up- stream.

This paper discloses the successful application of electron capture detector gas chrom- atography to the analysis of the minor com- ponents present in asphalts and their utility

to provide prima facie legal evidence, that is corroborated by other methods of identification.

EXPERIMENTAL

PROCEDURE

Collection

The oily, tar-like material was collected

by surface skimming of the water surface with

aid of a clean wide-mouth bottle. Source

samples were obtained from the asphalt pipe line; all samples were preserved in the refrigerator.

Extraction

The water samples (two grams of solid) were extracted with chromatographic grade chloroform

(200 ml) . Extracts were washed with water, dried over four grams of sodium sulfate and filtered.

The filtrate was collected in a 300 ml round

bottom distillation flask.

Concentration

The round bottom flask containing the dried

chloroform extract was attached to an all glass

distillation set-up; using a nitrogen ebullator

fitted to a Claisen head. The solvent was evaporated off at 200 mm pressure and collected

in a glass receiver leading to a dry ice trap

and then to the reduced pressure source.

Completeness of chloroform removal was monitored by disappearance of infrared absorption at 8.22u and 13.20u. Extracts of the source material and water samples were treated

similarly.

EQUIPMENT

Apparatus

The operating modes of the Perkin-Elmer 137 and 621 infrared spectrophotometers were given

previously (2,4). As asphalt petroleum samples

are tacky and viscous, thin-films were cast from

CHCl, solution or by warming of the asphalt and

the final thickness of the film was adjusted so that the^minimum transmittance of the peak at 1450 cm" lies in the range of 5 to 15%. Traces of chloroform may be monitored by noting the presence or absence of chloroform peaks.

For the electron capture detector gas chromatographic analysis, the Microtek (Tracer)

instrument with the Nickel 63 detector was used

as described previously (1).

Chemicals

All solvents were purchased from Burdick

and Jackson Laboratory, Inc. and reagents were

of special purity grade.

DERIVATIVE PREPARATION AND FRACTIONATION

One gram portions of the spill and source asphalt samples were extracted separately after

solution in chloroform (150 ml) using 5% alcohol KOH solution three times (150 ml).

The alkaline extract was acidified with 5% HCl in water and then extracted with CHCl^

three times (100 ml). This extract (100 ml) was stirred with 1.0 grams of powdered K2CO. and then refluxed in presence of excess pentafluorobenzyl bromide reagent in acetone (8% solution)

After one hour of reflux, the solvents were removed at 60°C/150 mm. The residue was again

taken up with 100 ml of CHCl^, shaken with 15 ml

of water in order to hydrolyze the esters. The

145
chloroform layer was dried with Na^SO^, and filtered. A 100 mg portion of the residue, con- taining traces of ether and thioether derivatives of phenols and mercaptans from the asphalt source and spill, was fractionated on

a 13 cm. silica gel column (6) filled with 34 grams of Davison 60/80 mesh particles, using

successive 100 ml volume of hexane, 10% benzene

in hexane, 30% benzene in hexane, 50% benzenehexane, benzene and ether. Six eluate fractions were collected for GC analysis involving use of electron capture detector.

INFRARED ANALYSIS

Both of the dried samples collected from

the source and the river sample were analyzed

with use of the Perkin-Elmer 137 infrared spec- trophotometer. Spectra were characterist jcally

similar Jhroughout the range from 660 cm' to 4000 cm . The spectra of the source and river

samples are shown to be similar by visual

examination. The two spectra are shown on Figures 1 and 2.

Table I. Infrared Ratios of Asphalts

Source - River

Ratio Absorbances

720 cm . 1375 cm

3050 cm

^ 2925 cm

810 cm

^ 1375 cm

810 cm . 720 cm

1600 cm . 1375 cm

1600 cm . 720 cm

Asphalt

Pipeline

.32

.30

.28

.86

.89

2.76

Asphalt found

in Ohio River

.32

.29

.29

,89

.83

2.53

4000 3000 2000

100

WAVELENGTH |MICRONS|

Figure 1. Infrared spectrum of source asphalt.

NAVELEIIGTII |MICIIONS|

Figure 2. Infrared spectrum of spill asphalt.

Evidence that the source and river samples,

are similar is demonstrated by infrared ratios taken of the two samples. These ratios are shown in Table I. A plot of the two key ratios,

-1 _ -1

810 cm 1375 cm

-1 vs

.

810 cm

720 cm

-1, obtained on numerous

industrial asphalts and No. 6 fuel oils yields

the graphical representation shown in Figure 3. The asphalt source ratio and spill ratio lie close-together, indicating identity. They are classified as asphalts as they are located within that group.

RATIO OF INFRARED ABSORBANCES

» LUBRICANT oil o HEAVY RESIDUAL FUEL OIL . 21 authentic industrial petroleum NO. 0 Fuel Oil

• ASPHALT, 19 authentic industrial samples

• ASPHALT, Samples from Transport Case !

1 2 3 Qin ru-1

720 CM'

Figure 3. Relationship of the spill and source asphalt among coimnercial asphalts and No. 6 fuel oils involving two R.I.A.'s.

CARBON- HYDROGEN ANALYSIS

In Table II are shown the carbon and hydrogen determinations of the pipeline asphalt

and the Ohio River sample.

Table II. Analysis of Asphalts, Source - River

Parameters

Carbon content % Hydrogen content

Asphaltene^'^-' %

Nickel (yg/g)

Vanadium (pg/g)

Za

Zo

Asphalt from Pipeline

85.57

10.86

21.1

81

30

-5.22735 -8.40503

Asphalt from Ohio River

86.07

11.16

22.6

4928

-4.68050

-S. 92630

146
.le values are averages of seven determinations per sample. This agreement of the carbon and hydrogen content of the pipeline asphalt with

the Ohio River sample indicates that the two samples are similar. Determinations were made

on the Hewlett-Packard 185B.

GAS CHROMATOGRAPHIC ANALYSIS

The following demonstration is proof that

the Ohio River sample is identical to the source

sample taken from the asphalt pipeline. To demonstrate that the two are similar, the weak

acid components (phenols and mercaptans) of the asphalts taken from the source and from the river were compared. Each asphalt mixture is treated with pentafluorobenzyl bromide and potassium carbonate in an acetone- chloroform mixture. Each reaction mixture is then fractionated

into six fractions using solvent mixtures of

varying polarity to effect a separation on silica gel column. The third eluate fraction

yielded the revealing electron capture detector

gas chromatograms , Figures 4 and 5.

MIHUIIS

Figure 4. Electron capture gas chromatogram of derivatives of weak acids from source asphalt

.

MINUTES

Figure 5. Electron capture gas chromatogram

of derivatives of weak acids from spill

asphalt.

The retention distance of the 14 resolved peaks

taken from the electron capture gas chromatographic analysis of the pentafluorobenzyl

derivatives of the asphalt pollutant from the Ohio River were compared to those from resolved

peaks of the derivative asphaltic material that

was taken from the asphalt pipeline. Fourteen

peaks (phenols and mercaptans) of the source

sample match the fourteen peaks (phenols and mercaptans) of the pollutant Ohio River sample.

All 28 retention distances were plotted as a 45° diagonal line showing excellent agreement of retention distances of the two samples. (Three

components of the 14 found in the source samples

are larger in amount than in the river sample; these may be lost as a result of solubilization,

etc.). The two asphalts are the same.

NICKEL AND VANADIUM RESULTS

The residue of asphalt resulting from the digestion in concentrated nitric acid was dis- solved in dilute nitric acid and analyzed by

atomic absorption. The nickel and vanadium

contents in the source sample were 81 and 30 mg

per gram, and these values in the river sample

were 49 and 28 mg per gram, respectively. The nickel in the river sample appears to be some- what lower than expected, whereas the vanadium

results agree well (Table II).

DATA TREATMENT AND STATISTICAL ANALYSIS

Infrared spectrophotometry has been a useful technique for the characterization and identification of these materials. With the use of a combination of infrared spectrophotometry, data

treatment, data transformation, and discriminant

function analysis with computer assistance, a precise method of classification has been derived

(5). From ajnong 20-plus samples of commercial

asphalts, the unknown river sample was coupled

to the commercial source via good agreement of

mathematical values from the corresponding

linear discriminant functions (5) as indicated

by the Za's values in Table II. Za and Zo are the linear discriminant function values of asphalt and heavy residual fuel oil, respectively. The higher algebraic values belong to Za's. Therefore, both are asphalts. In addition, the fairly close agreement of the Za's values of the source and spill asphalt

indicates reasonable identification.

ENFORCEMENT ACTION

The Coast Guard won its case. All results pointed to the conclusion that the pipeline

asphalt was the source of the pollutant river

asphalt.

References

[1] Kawahara, F.K., "Microdetermination of Derivatives of Phenol and Mercaptans by

Means of Electron Capture Gas Chromatography," Analytical Chemistry, 40, 1009

(1968) .

[2] Kawahara, F.K., "Characterization and Identification of Spilled Residual Fuel

147
Oils by Gas Chromatography and Infrared

Spectrophotometry," Journal of Chroma- tographic Science, 10, 629 (1972).

[3] Abraham, H., "Asphalt and Allied Sub- stances, Industrial Raw Bituminous

Materials," Volume IV, 294 (1960). D Van Nostrand Co., Inc., Princeton, N.J.

[4] Kawahara, F.K., and Ballinger, D.G.,

"Characterization of Oil Slicks on Surface Waters," Industrial and Engineering

Chemistry, Product Research and Development,

9, 553 (1970).

[5] Kawahara, F.K., Santner, J.F., and Julian,

E.C., "Characterization of Heavy Residual

Fuel Oils and Asphalts by Infrared Spectrophotometry Using Statistical Discriminant

Function Analysis," Analytical Chemistry,

46, (February 1974)

[6] Breidenbach, A.W., Lichtenberg, J.J., I Henke, C.F., Smith, D.J., Eichelberger, J.

'

W. and Stierli, H., "The Identification and I Measurement of Chlorinated Pesticides in

' Surface Waters," U.S. Dept. of Interior, [ FWPCA, WP-22, November 1966. |

I

Key Words: Asphalts; Characterization;

Computers; Discriminant Function Analysis;

Gas Chromatography; Heavy Oils; Identifications;

Infrared Analysis; Minor Component Analysis;

Oil Spills.

148
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthers

burg, Maryland, May 13-17, 1974 (Issued December 1974).

IDENTIFICATION OF HYDROCARBONS IN AN EXTRACT FROM ESTUARINE WATER

ACCOMMODATED NO. 2 FUEL OIL

R. H. Bieri , Ann L. Walker , B. W. Lewis , G. Losser and R. J. Huggett

Environmental Chemistry Section

Virginia Institute of Marine Science

Gloucester Point, Virginia 23062

U. S. A.

Northrop Service Corporation

NASA, Hampton, Virginia 23665

U. S. A.

NASA-Langley Research Center

Hampton, Virginia 23665

U. S. A.

Introduction

The traditional use of the oceans,

estuaries and other large bodies of water,

mainly as a source of food, is increasingly being challenged by other large

scale technological operations typical of

modem civilization. At the same time,

there is a growing need to develop the

maximum potential of the oceans as a source of protein. In the shaping battle

between the different interests, it is of

utmost importance that the scientific

community has the sound, basic knowledge

necessary to understand the possible interferences of such technological uses with marine food production.

Of concern here are the fossil hydrocarbons and activities capable of affecting their composition and distribution in

the environment. Considering the extreme

complexity of such mixtures and the re- sulting complex interactions with the

biota, it is clear that a sufficient

scientific knowledge base can only be

reached within reasonable time by the

proper combination of maximum efficiency

and analytical limitation. Since analytical limitation is inherent even with

the most sophisticated methods of analysis, only those capable of providing a maximum of information and those which

lend themselves to computerized data

acquisition and interpretation should be

used: the mass spectrometer with interfaced gas chromatograph and data handling

system. The application of such a system to a problem of hydrocarbon analysis

is described.

Analysis of an extract of a No. 2 fuel oil

accommodated to wateiT

A commercial grade No. 2 fuel oil

(Gulf) was accommodated to filtered and

pre-extracted York River water at room

temperature, extracted with methylene chloride [1] in one experiment and with n-heptane t2l in another. These extracts were

then submitted to analysis in a computerized GC-MS system with repetitive scan

(Finnigan, 1015). Aliquots of the extracts were also used to derive chromatograms

using Apiezon L as the stationary phase.

To demonstrate the compositional changes

occurring in the water accommodation step

[3] , chromatograms were also derived from

straight No. 2 fuel oil, from a 5A molecular sieve accommodated fraction of No. 2 fuel oil and from the residual fraction of

the molecular sieve treated fuel oil.

Figure la shows the general features

of the No. 2 fuel oil; a broad, unresolved

envelope with a boiling range extending

from about 170° C to 360° C. Superimposed

on this envelope are distinct peaks, mainly the n-alkanes (fig. lb), the isoprenoid

pristane (peak No. 40, fig. la), plus a number of aromatic compounds, mainly substituted benzenes, 1, 2, 3, 4-tetrahydronaphthalenes and naphthalenes

.

R.I.— 2000 r900 (600 iTOO 1600 1500 1400 1300 1200 llOO 1000 900 800

R. I. *- 2100 2000 1900 1800 1700 1600 1500 ("SOO i300 1200 1100 lOOO 900 Figure la. Commercial No. 2 fuel oil.

Numbers refer to corresponding peaks.

Abszissa identifies retention indices,

lb. N-alkanes separated from the same

fuel oil. Column data: 3% Apiezon L,

80-100 chrom."W-AW, •>,v, _T.7_AI.7 ss^„ 8

Q 11/2^ /O' jj 1/16"

5.6 cc/min N2

149
In figure 2, the fractionating effect

of the water on the oil is clearly demonstrated. Chromatogram 2a is again from

No. 2 fuel oil and 2b is from the extract

of the water accommodated phase. The un- resolved envelope in the extract is almost

absent, the main n-alkane peaks have disappeared or are hidden in the large peaks now practically all consisting of aromatic compounds. Identifications in these

low resolution chromatograms must be

viewed with caution, as many of the peaks

contain several compounds. Where reference to compound types or specific com- pounds is made, it is supported by information from Scot columns and mass spectrometric information. The most prominent

peaks are the substituted tetralins (20,

22,24), tetralin (17), biphenyl (29), the

substituted naphthalenes (30,31,32),

methyl indane (16) and substituted ben- zenes (0, 1, 2, 6, 7, 8, 13 and 15). Although precise solubilities for most of

these compounds are not available, estimates based on empirical relationships

[41 suggest that the concentrations of

the substituted benzenes in the water

tend to follow the solubilities.

The "aromatization" of No. 2 fuel oil

upon uptake by water is again seen in

figure 3. The top chromatogram (fig. 3a)

is the water extract, the bottom chromatogram (fig. 3b) is derived from No. 2 fuel oil by subtraction of all compounds

accommodated by 5A molecular sieve. The

ni »- 2000 1900 leoo i^oo leoo imx> 1400 noo >200 iioo 1000 900 eoo Figure 2a. Same as la. 2b. Methylene chloride extract of York

River water accommodated No. 2 iuel oil.

Column data are the same as in fig. 1.

HI — 2000 1900 IBOO l?tX) 1600 1500 lOOO 1500 1330 IWO lOOO 900 900

b

R 1 «- 2000 1900 1900 ITOO I6O0 1500 1400 1300 1200 HOO 1000 900 800 Figure 3a. Same as 2b.

3b. No . 2 fuel oil minus n-alkanes (and

other compounds which are accommodated

by 5A molecular sieve). Column data

as in fig. 1. two chromatograms differ mainly in the

large unresolved envelope. Most of the

peaks, except for differences in intensity,

are identical in both chromatograms . It should be mentioned that all chromatograms

from samples involving a solvint evaporation step are distorted (co-i;vaporation

of volatile compounds) and that the actual

concentrations of substituted benzenes and

indanes in the original samples are considerably higher. In a typical oil spill

situation, however, such losses may also occur because of the competition between

the relatively fast evaporation and the

diffusion limited solubilization at the

interface

.

The detailed characterization of the

water extracts led to the identifications

shown in Tables I-III. Two different

liquid phases were necessary to produce

the displayed detail. Most of the monoaromatics were identified from runs using

a DDF coated Scot column (100' x 0.02",

1.5 cc/min helium flow) and the condensed

aromat_cs from a Scot column with OV-25 as the stationary phase (50' x 0.02", 1.5

cc/min heliiam flow)

.

Table I shows the alkylbenzenes identified in the water extract. The most

reliable identifications are those based

on standard samples and are listed under

a. Those labeled b have been identified

Trom spectra in the Aldermaston collection

150
TABLE I. BENZENE COMPOUNDS FOUND IN A MFfHYLENE CHLORIDE EXTRACT OF AN ESTUARINE

WATER ACCOMMODATE OF A NO. 2 FUEL OIL BY GC - MS

MONOSUBSTITUTED BENZENES, C^ to C^q

a ETHYLBENZENE T n-PROPVLBENZENE T ISOPROPVLBENZENE T SEC-BUTYIBENZENE T ISOBUTYLBENZENE T BISUBSTITUTED BENZENES, C„ to C

10

a 0 - XYLENE m - XYLENE

p

- XYLENE

0 - DIETHYLBENZENE m -DIETHYLBENZENE T

p

- DIETHYLBENZENE

0 - ETHYLTOLUENE m -ETHYLTOLUENE

p

- ETHYLTOLUENE

b o-n- PROPYLTOLUENE

p-n-PROPYLTOLUENE

0 - ISOPROPYLTOLUENE T m - ISOPROPYLTOLUENE

p

- ISOPROPYLTOLUENE T

TRISUBSTITUTED BENZENES, C^ & C^^

a 1,2,3 - TRIMETHYLBENZENE

1.2.4 - TRIMETHYLBENZENE

1.3.5 - TRIMETHYLBENZENE

b 1,2 - DIMETHYL-3-ETHYLBENZENE

1.2 - DIMETHYL-4-ETHYLBENZENE

1.3 - DIMETHYL-2-ETHYLBENZENE

1,3 - DIMETHYL -4-ETHYLBENZENE

1.4 - DIMETHYL-2-ETHYLBENZENE

TETRASUBSTITUTED BENZENES, C

10

a 1,2,4,5 - TETRAMETHYLBENZENE

b 1,2,3,4 - TETRAMETHYLBENZENE

1,2,3,5 - TETRAMETHYLBENZENE

C,,& C,„ ISOMERS SEPARATED, NOT SPECIFICALLY

IDENTIFIED

NO.

c C

5 SUBSTITUTED BENZENES 16 SUBSTITUTED BENZENE T 1

= TRACE, M = MAJOR CONSTITUENT

INDICATES IDENTIFICATION BY COMPARISON WITH STANDARDS RUN ON SAME GC - MS

IDENTIFIED BY B.P. & GC RETENTION TIME DATA AND COMPARISON WITH M. S. DATA IN LITERATURE CORRELATED WITH M.S. LITERATURE DATA

and have been structually labeled according to their boiling points. Listings

under c, finally, are identifications

based on mass sprctra alone. Admittedly,

some of the ideatiiications labeled b and

£ may not be definitive, as in some cases

the mass spectra elone may not be specific

enough to identify the compound, or assumed retention trends may prove to be

invalid. Where compounds have been separated and partially identified, we did

not have adequate information to specify

the substituent groups in detail. It is

certain that some of these ambiguities

will be corrected as work progresses.

In Table I, it is noted that all

isomers of diethyl-, methyl- ethyl-,

methyl-isopropyl-, trimethyl- and tetramethylbenzene were found. All dimethylethylbenzenes except the 1, 3-5 isomer were identified. Altogether 30 substituted benzenes were identified and 17 more

isomers were separated and partially

identified but could not be further

charac terized

.

Table II shows the naphthalenes and

1, 2, 3, 4-tetrahydronaphthalenes,

again with the mode of identification.

The monoalkylnaphthalenes containing

either a methyl or ethyl group are complete. Four of the 10 possible isomers

of dimethylnaphthalene are not identified

with respect to their structure, but 2 mere were separated. The missing two

iKomers were either not present above the

detection level or were co-eluting with

a relatively abundant compound. Only two

of the 15 possible trimethylnaphthalenes

could be specifically identified; more may be among the 7 separated C3 - isomers.

All naphthalenes of either higfler substitution or molecular weight ren-iain of un- known specific structure because their mass spectra do not allow further distinction. All of the possible methyltetralins were identified and together

with the tetralin they belong t.o the most

prominent compounds found in the watei:

extracts. Ethyl-, dimethyl- and trimethyltetralins were separated and identified by their mass spectra, but no specific structure could be assigned. Thus,

18 naphthalenes and tetralins could be

characterized completely, while 30 more

were separated and partially identified.

151
TABLE II. NAPHTHALENE COMPOUNDS FOUND IN A METHYLENECHLORIDE OR HEPTANE EXTRACT

OF AN ESTUARINE WATER ACCOMMODATE OF A NO. 2 FUEL OIL BY GC-MS

a NAPHTHALENE, C^q Hg

MONOSUBSTITUTED NAPHTHALENES, C^^ &

a 1- METHYLNAPHTHALENE

2- METHYLNAPHTHALENE M

1- ETHYLNAPHTHALENE

2- ETHYLNAPHTHALENE

BISUBSTITUTED NAPHTHALENES, C

12

1,6,& 1,3 - DIMETHYLNAPHTHALENE

1.5 - DIMETHYLNAPHTHALENE

2.6 - DIMETHYLNAPHTHALENE

2.3 - DIMETHYLNAPHTHALENE

1.4 - DIMETHYLNAPHTHALENE

M

TRISUBSTITUTED NAPHTHALENES, C

13

a 2,3,5 - TRIMETHYLNAPHTHALENE

2,3,6 - TRIMETHYLNAPHTHALENE

C,„ to C,.ISOMERS SEPARATED, NOT SPECIFICALLY

IDENTIFIED „^NO.

c DIMETHYLNAPHTHALENES 2 C,-SUBST'D. NAPHTHALENES 7 Cj-SUBST'D. NAPHTHALENES 8 Cj-SUBST'D. NAPHTHALENE 1

1, 2, 3, 4-TETRAHYDRONAPHTHALENES (TETRALINS)

b 1,2,3.4-TETRAHYDRONAPHTHALENE,CjqHj2

MONOSUBSTITUTED TETRALINS, C,11

b I - METHYLTETRALIN

2 - METHYLTETRALIN

5 - METHYLTETRALIN

6 - METHYLTETRALIN

M

M

M

C,p& C,^ ISOMERS SEPARATED, NOT SPECIFICALLY

IDENTIFIED

ETHYLTETRALIN DIMETHYLTETRALINS

TRIMETHYLTETRALIN

Cj-SUBST'D TETRALIN

NO.

19

1

1

Table III contains the indanes, biphenyls and a few polyaromatic compounds

plus some of their alkylated forms. Most

of the latter must remain unidentified

with respect to their detailed structure

for reasons mentioned above. Also present are the n-alkanes from decane to tridecane, and finally a few other com- pounds which include the only hetrocompound identified (dibenzofuran) . It should be noted that biphenyl was one of

the most abundant compounds . A total of

18 identified compounds appear on this

list and 28 other isomers were separated

and partially identified.

This presentation demonstrates the

potential application of computerized

GC-MS systems to environmental problems

involving complex hydrocarbon mixtures.

It contains several shortcomings. The

chromatograms for the figures, for instance, were derived from packed Apiezon

L columns, while they should have been

recorded from the same columns used to derive the mass spectra. Ideally, the

retention data should be stored in the

computer and used as complementary information for the computer assisted interpretation of mass spectra 151. Identifications have been made by extensive use of

computer derived mass chromatograms [6]

and manual interpretation and thus have

been too time consuming. Future plans include computer mass spectral matching and

quantitative estimation by GO methods.

It is considered that the shortcomings can

all be resolved and that the kind of information mentioned at the beginning of this

paper will be forthcoming with sufficient

time and effort.

References

Ell Hites, R. A. and Biemann, K. , Science,

178, pp 158-160 (1972).

E2] Peake, Eric, and Hodgson, G. W., J. Am. Oil Chem. Soc . , 44, pp 696-702

(1967).

E31 Boy Ian, D. B. and Tripp, B. W. , Nature

230, pp 44-47 (1971).

E41 McAuliffe, Clayton, J. Phys. Chem.

70, pp 1267-1275 (1966).

152
TABLE III. INDANES. BIPHENYLS, AND OTHER ORGANICS FOUND IN A METHYLENECHLORIDE EXTRACT OF AN ESTUARINE WATER ACCOMMODATE OF A NO. 2 FUEL OIL BY GC-MS

INDANES, Cg to C^

niuni-[\ uvji>iuLiMOLL' ixiiMU n I ui\wv/rM\ DvjiN J , 1^2^^ 15

b INDANE, CqH,^ T

1- METHYLINDANE

a ACENAPHTHENE C^^H^^

2- METHYLINDANE FLUORENE, Cj^jH^q

ISOMERS SEPARATED, NOT SPECIFICALLY ANTHRACENE, C^^H^q

IDENTIFIED

IMU. c METHYLINDANES 2 ISOMERS SEPARATED, NOT SPECIFICALLY IDENTIFIED

NO. ETHYLINDANE 1 c METHYLFLUORENES 4 DIMETHYLIN DANES 6 r -SIIRST'D FIllORENES Methylanthracenes

34 BIPHENYLS, Cj2 ^° ^13 s^ATIIDATFn AITPHATTP HVDRnPA RRONK C tn P

a BIPHENYL, C^^H^^ ^

b 2 - METHYLBIPHENYL

3 - METHYLBIPHENYL

a n - DECANE, C^^H^^

nII - IIMDFrAMF UIM ULunlNL, C H

24 4 - METHYLBIPHENYL n - DO DECANE, C^2H26

ISOMERS SEPARATED, NOT SPECIFICALLY

IDENTIFIED

- NO.

3

b n - TRIDECANE, C^^H^^

c DIMETHYLBIPHENYLS

other ORGANICS, C^^ ^° ^14 C„-SUBST'D BIPHENYLS

C^-SUBST'D BIPHENYLS

2

3

a DIBENZOFURAN, C^^H^O

DIPHENYLMETHANE, C^jHj2

c_ PHENYLCYCLOHEXANE, C^^H^^

1,1 - DIPHENYLETHENE,C^^H^2 T

LSI Nau, H. and Biemann, K. 46, pp 426-434 (1974).

161 Kites, R. A. and Biemann, K.

,

Chem., 42, pp 855-860 (1970)!

Anal. Chem., Key Words: Computer, Fossil hydrocarbons, No. 2 fuel oil. Gas chromatograms

,

Mass spectrometry. Specific compound

Anal. identification. Water accommodate.

153

TOPICAL SESSION III. Standards and Intercomparison Criteria

155

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

THE ROLE OF STANDARD REFERENCE MATERIALS

IN ENVIRONMENTAL MONITORING

H. Thomas Yolken

Office of Standard Reference Materials

National Bureau of Standards

Washington, D.C. 20234

This paper describes meaningful mea- surements and how they are obtained; some

of the factors that go into making a mean- ingful measurement; and the role that NBSStandard Reference Materials (SRM's) play

in that effort. In addition, the philosophy of certification of NBS-SRM's is given

followed by a short description of cur- rently available and planned NBS environmental SRM's, and the possibility of NBS

producing trace crude oil constituent

SRM's.

The goal in any measurement is to produce meaningful data - - for data to be

meaningful it should be accurate, precise,

and specific. Figure 1 has been used with

some success as an analogy to explain the

difference between accuracy and precision:

Three imaginary marksmen fire a rifle at a target. In the top target, the marksman

is both imprecise and inaccurate. The

marksman is quite precise but inaccurate

in the middle target, and in the bottom

target, the marksman is both accurate and

precise. Of course, the analogy in all cases is that the bull's eye corresponds

to the target value or "true" value.

An inaccurate and

imprecise marksman

An inaccurate but precise marltsman

An accurate and

precise maritsman

No statement of

potential accuracy

possible

Potentially accurate Find source of systematic error

Accuracy cannot be

attained until precision is first achieved

Bull's-eye corresponds to target value or 'true' value

Figure 1. Accuracy and Precision

Turning to specificity, the determination of strontium in granite done at NBS several years ago is an interesting

example of the meaning of specificity.

The results obtained by two different

methods are shown in figure 2: 1.0 ppm

Sr obtained by atomic absorption with a standard deviation of ±10 percent; and

17.0 ppm Sr obtained by neutron activation

analysis with a standard deviation of

±5 percent. Which result is closer to the

bull's eye? In this case, the atomic absorption results were more accurate even though they had a standard deviation twice

that of the neutron activation analysis

measurements

.

WHICH IS THE BEST METHOD?

Atomic Absorption

' ' slot

1 0 ppm Sr ^

^^\^^^^^ Neutron Acti valion

17 0 ppm Sr

STRONTIUM IN GRANITE

Figure 2. Strontium in Granite

The reason for the larger error in the

neutron activation analysis results was, non-specificity of the technique. The

granite besides containing Sr, also con- tained uranium-235 which fissioned on irradiation with neutrons to give an additional apparent 16 ppm Sr, as shown by

figure 3.

NBS-SRM's are designed to be tools to help insure meaningful measurement. An

NBS-SRM is defined as a well-characterized

material, produced in quantity and certified by NBS to help: calibrate instruments, develop reference methods of mea- surement, and provide long-term quality

control in a measurement system. It should be noted that NBS has a congressional mandate to provide nationally

authoritative SRM's.

One of the most important facts built

into most NBS-SRM's is known accuracy.

The accuracy of an NBS-SRM is generally

established by one or more of three routes

to certification. These three routes are arranged in order of preference and are:

157
SYSTEMATIC ERROR - THE VILLAIN LEAD IN 500 PPM GLASS

The Strontium contained in the granite is made radioactive by

irradiation with neutrons and the radioactive Sr is then counted and the original Sr content calculated: Thus:

""Sr + n—''Sr-^— ''y (stable) o4d

BUT (the villain) granite contains uranium and

fission 89„ ^ 'U + n » Srproducts 54d

Y (stable)

And there is no physical way of differentiating the Sr formed

from the uranium from that formed from the natural occurring strontium.

1 ppm U gives an apparent 16 ppm Sr

Figure 3. Systematic Error

refererence method, two independent methods, or round robin tests. The preferred

route to certification is by a reference

method, which is a method of known or proven accuracy. Its use assures the ac- curacy of the determination if personal

bias is eliminated. This is eliminated

by having the measurements made, when

possible, by two or more analysts.

The second route to certification is

used when a reference method is not available. The route requires the use of two

or more independent methods. Each of these

independent methods must have estimated

systematic biases that are small relative

to the accuracy goal set for certification.

The first two routes are subject to critical scientific review through statistical analysis of the data obtained. This,

however, may not be the case for the third

or round robin route, which may be subject

to a somewhat less rigorous analysis of

the data. The case can be made that this

route is valid because in a system under

good quality control, (based on accuracy)

it works.

The following examples illustrate

the certification of NBS-SRM's using each

of these three routes. NBS has issued a series of glass SRM's certified for trace

elements at levels from 0.02 to 500 ppm.

The lead content of these SRM's was certified using isotope dilution thermal ion source mass spectrometry, which is a recognized method of known and proven ac- curacy for lead. Similar standard deviations were obtained using this method

by two analysts working 2,000 miles apart,

(fig. 4). These results are important

as they signify that the system was under

control. The certified value of

426 ± 1 ppm for lead is a conservative

Rod No.

2

13

18 48

56

66

78 106

Average

(J

Analyst 1

426.5

426.2

425.6

426.1 426.9

426.0

426.2

425.7

426.15 i0.41

Analyst 2

425.9

426.0

425.0

425.4

425.6

425.58

±0.40

Figure 4. Lead in Glass SRM

figure that provides for possible un- known sources of systematic error.

As an example of the second route,

three independent methods of analysis were used to determine cadmium in SRM 1577,

Bovine Liver. Isotope dilution spark

source mass spectrometry, atomic absorption, and polarography gave 0.28, 0.27 and

0.25 ppm, respectively, with the certified value being at 0.27 ± .04, (fig. 5).

CERTIFICATION BY TWO OR MORE

INDEPENDENT METHODS

Cadmium in Bovine Liver

Sample ID-MS Atomic Absorpt Polarography

1 0.32

0.29

0.29

2

3

0.26

0.27

0.27 0.27

0.24

0.26

0.26

0.27

0.26

0.16*

4

5

0.28 0.24

0.27 0.30

0.28

0.28

6 0.26 0.26 Id

0.28 0.27 0.25 0.04 0.04 0.11 Range (all results) 0.24 - 0.32

I Recommended Value 0.27+ 0.04 |

Figure 5. Cadmium in Liver SRM

In this case it is not a reference method

as was the case for lead because the systematic errors have not be exhaustively

studied for Cd. The third route to certification, inter laboratory testing, is shown in figure 6. This round robin involved six different, highly competent

158
CERTIFICATION BY CONSENSUS SRM 337 - Basic Open-Hearth Steel Carbon METHOD/VARIATION

(Note: Combustion step common to all) %

CARBON

1 Gravimetric — 1 g sample 1.08

2 Gravimetric — 3 g sample 1.06

2 Volumetric — 1 g sample 1.06

3 fir;)vtfTiptrir Ul a VIIIICII lb pArtnr lOblUI wpinht VVCiyilL 10\i. . T\1 tj n\ cnmnip yj OulllUIC 1.06

3 Gasometric ~ 1 g sample 1.07 4 Gravimetric - Half-factor weight (1.36 g) sample 1.06

5 Gravimetric - Half-factor weight (1.36 g) sample 1.08

5 Thermal Conductivity 0.7 g sample 1.08 6 Gravimetric - 0.7 g sample 1.07 Mean 1.07

Figure 6. Carbon in Steel SRM

laboratories in the determination of the

carbon content of a steel SRM. Although

four different methods and six different

sample weights were used, highly satisfactory results were obtained. It should

be noted, however, that a previously issued NBS-SRM, similar to the material

under study, was required for internal

quality control in each of the laboratories. The use of the round robin approach

should only be used for measurement sys- tems or fields of science and technology

that have already obtained good quality

control. Several reasons exist for avoiding the round robin approach. First, a field may not be ready for it, as the

field is not in good quality control.

Secondly, that the proper constraints,

i.e., sampling procedures, statistical

interpretation of the data, etc., may not

be rigorously applied. An illustration of

the danger in the round robin approach can

be seen (fig. 7) from the wide range of

values reported by different laboratories

for various elements in this orchard

leaves SRM. These data could not be used

for certification! This SRM was actually

CERTIFICATION BY CONSENSUS

A DANGER

Orchard Leaves

Element

Determined

No. of Labs Mean

X

Range S/X%

P 10 0.20% 0.14 - 0.24 25

Al 10 222/ig/g 99 - 401 36

Fe 11 239;Ltg/g 151 - 367 28

Mo 5 5.4 ^g/g 2.3 - 10.5 59

certified for some 14 different elements

using the second route.

An important segment of the U.S. mea- surement system, is dependent on SRM's.

For SRM's to be most effective, they need

to be integrated in this or a similar system. Figure 8 shows the parts of the U.S.

measurement system and how they tie the

first link in this measurement system,

and form the common foundation for all

quantitative measurement systems. Fortunately, these units have been agreed upon

internationally, and are called SI units

from the Systeme International de Unites

(International System of Units) . Producing and distributing certified SRM's on a national basis is the next link to the

measurement chain. In the U.S., this is

mainly the job of NBS, as has been prescribed by congressional legislation.

Other organizations produce calibration

materials in their particular field of

science or technology. An example of this

is the U.S. Geological Survey, which produces geological samples. The next link

in this system is reference methodology.

A reference method of measurement is

defined at NBS as a method of known and

demonstrated accuracy. In addition, the

accuracy inherent in the method has been

shown to be transferable by interlaboratory testing.

MEANINGFUL MEASUREMENT SYSTEM IN THE U.S.A.

BASE AKD

DERIVED UNITS I

1 SRM'S 1 REFERENCE MnHODS

QUALITY CONTROL

ASSURANCE

FIELD METHODS |

WORKING

STANDARDS

MEASUREMENTS

THAT ARE ACCURATE

PRECISE

SPECIFIC

Figure 8. U.S. Meaningful Measurement

System

Figure 7. Orchard Leaves SRM

The base and derived units and SRM's

are the direct responsibility of NBS.

This is not the case for reference methods,

NBS becomes involved in reference methods

only when outside organizations have not

or cannot develop reference methods by

themselves. However, many collaborative

efforts do exist between NBS and profes159
sional societies, standards bodies, trade

associations, and other Government

agencies to provide SRM's and reference

methods. An example of NBS involvement in

such work is the development of a reference method for the determination of

calcium in serum [1]

.

Primary SRM's and reference methods

do not find wide-spread daily use in mea- surement laboratories. But they tie

directly to the next link in the system - - the field methods of test and working or everyday calibration standards. When used

together, reference methods and NBS-SRM's

provide organizations with the means to evaluate their working standards and field

methods of test. As a consequence they

allow measurements to be based on accuracy.

From this network, measurements are produced that are meaningful in terms of

accuracy and precision. One more part is

needed to insure that the system works

smoothly and produces the desired results

over a long period of time. A quality control assurance program involving interlaboratory testing with unknown samples and

analysis of the results as evaluated

against SRM's and reference methods fulfills this need. Quality control assurance programs are sponsored in the U.S. by many different organizations. However,

they are not always based on SRM's and

reference methods. As a result, some of

these quality assurance programs give a measure of between- laboratory precision

only

.

The description of how NBS-SRM's are certified and how they fit into the mea- surement system provides a suitable introduction to a group of NBS-SRM's specifically designed to meet the somewhat

lengthy measurement-needs for environmental work. What environmental SRM's are currently available from NBS? The

complete list of currently available

environmental SRM's is given in the SRM

Catalog [2] which can be obtained from

NBS free-of -charge

.

Gaseous SRM's in stock include propane, carbon monoxide, and carbon dioxide for engine exhaust monitoring and

standard air certified for oxygen content.

The standard air is used to monitor longterm oxygen trends in the atmosphere and

to detect any changes in the air's oxygen

content. In addition, sulfur dioxide permeation tubes are available that have been

certified for their SO2 permeation rate.

In the fuels area we have residual

and distillate fuel oils and coal certified for their sulfur content at several

concentrations. Thus, the problem of SOlevels in the air is addressed from two points; before burning (fuels) and afterward (permeation tubes)

.

Another coal SRM is certified for

trace concentrations of mercury; while

two biological SRM's, orchard leaves

and bovine liver, are certified for trace

amounts of toxic heavy metals. And

finally, a large number of radioactive

SRM's are available for monitoring the

air, water, and solids around nuclear

power plants and fuel reprocessing

facilities

.

The following SRM's are now in the

development or production stages at NBS:

urban air particulate (heavy metals);

lead in gasoline; mercury in water; mercury

in tuna fish; river sediment (radioactivity); NO2 permeation tube; nitric oxide in

nitrogenf coal, fly ash, and fuel oil

(trace elements)

.

What environmental SRM's are planned

for the future? Specifically, what about

NBS-SRM's certified for trace amounts of

the constituents of crude oil? Hopefully,

the needs for these SRM's can be well defined in terms of which crude oil constituents, at what concentrations in which

natural matrices are needed. Obviously,

since SRM's cannot be made for every possible combination, the problem must be

approached by developing several "bench

mark" SRM's that can be used to tie the

field together. For example, one could

envision a biological material set of

SRM's, a botanical materials set of SRM's,

a sediment or soil set of SRM's and perhaps an aqueous set of SRM's. Each of

the same material with several concen- tration levels for one or more crude oil

constituents. Of course, the stability,

size, and number of each SRM to prepare

based on expected sales are questions that

also need to be answered before NBS can begin to produce these SRM's. The need for

SRM's in the whole area of water pollution

is considered to be extremely important.

NBS is currently surveying the field with

a questionnaire to determine which SRM's

have the highest priority.

References

:

[1] Cali, J. P., Mandel, J., and Moore,

L., Standard Reference Materials: A

Referee Method for the Determination

of Calcium in Serum, NBS Spec. Publ.

260-36, NTIS Number COM 72-50527,

Springfield, Virginia 22151.

[2] Office of Standard Reference Materials, Standard Reference Materials:

1973 Catalog, NBS Spec. Publ. 260,

U.S. Government Printing Office,

Washington, D.C. 20402 (1973).

Key Words: Accuracy; environmental

monitoring; marine pollution; NBS-Standard

Reference Materials; water pollution.

160
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

STANDARD AND INTERCOMPARISON CRITERIA: TAR BALLS AND PARTICULATE MATTER

Richard W. Traxler

Richard H. Pierce, Jr.

College of Resource Development

University of Rhode Island Kingston, Rhode Island 02881

The study of tar balls and particulate matter

Is important in determining the fate of petroleum

in the marine environment. Ideally, scientists

interested in various aspects of petroleum pollution should be able to rely on published data for comparison of results. Unfortunately, one cannot make comparisons with certainty, because the results from even the same sample may vary according to the analytical procedure used.

Appropriate standards and blanks are basic to good experimental design, but the need for intercomparison of analytical procedures has not been

so readily recognized. The feasibility of intercomparison standards has been recently demonstrated by Farrington et al (1) . In addition to the use of intercomparison standards, it would be desirable to devise guidelines to help standardize analytical procedures and to limit the number

of different techniques.

We are Involved in a study of the fate of a #6 fuel oil spilled In Narragansett Bay, R.I. Certain aspects of our study may be used to exemplify the need for adequate standards and intercomparison procedures.

The adequacy of the analytical procedure to follow changes in the aliphatic and aromatic hydrocarbon fractions of the spilled oil was determined by carrying various standard hydrocarbons

through the extraction, clean-up, fractionation

and analysis procedure. A series of n-alkanes,

branched and cyclic aliphatic hydrocarbons and aromatic hydrocarbons were tested. A wide variety

of compounds was used to detect differential re- coveries of the various petroleum components due

to differences in solubility and volatility.

Along with quantifying the recovery of standards, blanks are especially important when ana- lyzing particulate matter. The low concentration

of petroleum associated with particulate matter

requires very high concentration factors which

greatly magnify contaminants.

To determine how the results from our analytical procedure compared with others, a sample of

the //6 fuel oil was sent to Dr. James G. Quinn at the University of Rhode Island, Graduate School

of Oceanography. A comparison of our analysis of

the #6 fuel oil (fig. 1) with that of Quinn and Wade (Unpublished Data) (fig. 2) shows how different analytical procedures may produce dissimilar

chromatograms for the sample (The predominent peaks

in fig. 2 corresponding to 190 °C and 220 °C are

internal standard hydrocarbons n-C22 and phenanthrene )

,

A tar ball resulting from the oil spill (fig.

3) was analyzed In our laboratory for comparison

with the //6 fuel oil data. Using our data (fig.

1) we can identify the //6 fuel oil as the source

of the tar ball with considerable certainty, however, we could not make the identity by comparing

Inc. Temp. °C

Figure 1

No. 6 Fuel Oil

- PENNANT-

( Quinn and Wade )

250 Inc. Temp. C

Figure 2

Inc. Temp. °C

Figure 3

161
our tar ball chromatogram with the #6 fuel oil chromatogram of Quinn and Wade (fig. 2). The difference in the results of the #6 fuel oil analyses was due primarily to different conditions during GC analysis. The procedure of Quinn

and Wade included TLC to separate the aliphatic and aromatic hydrocarbon fractions (Table I) and GC analysis using a column of 12% FFAP on 80/100 mesh

Chromosorb WHP, temperature programmed from 150 °C to 250 °C at 8 °/min. Our procedure used column chromatography for separation of these components

(Table l) and GC analysis with a column of 3% SP-2100 on 100/120 Supelcoport , temperature pro- grammed from 100 to 275 °C at 6 °/min. A column

of 12% FFAP was also used in our proced\ire to provide a separation of n-alkane and isoprenoid

hydrocarbons

Although the chromatograms show dissimilar

patterns under these different GC analytical proced\ires, a more involved comparison of select characteristics of the chromatograms provided a good correlation of our results with Quinn and Wade

(Table I). Thus it is possible to correlate data obtained by different methods if it is known how

the analytical procedures compare.

Table I. A Comparison of Results from Different

Analyses of a #6 Fuel Oil.

% Aliphatic

% Aromatic

n-Cj^^/prlstane

pristane/phytane

Pierce & Traxler Quinn & Wade

87^

13a

1.8^ 1.0^

89'' lit

1.0''

a Column

b Column

3% SP-2100

12% FFAP

may be the most critical portion of petroleum con- cerning toxicity, carcinogenicity and persistence,

cannot be analyzed by GC. More emphasis is needed

on high speed liquid chromatography and various

detection and data retrieval systems for the asphaltic fraction, such as those discussed by

Gruenfeld (3).

Solving problems of petroleum pollution requires input from studies ucilizing relatively

simple techniques as well as extremely sophisticated instrumentation. The exact procedure used

is not as important as knowing how the procedure

compares with others and recognizing the limitations .

To allow for proper intercomparison of data,

it is essential to agree on certain guidelines to follow during petroleum analysis.

In general, the purpose for standards and intercomparison is to determine the adequacy of an analytical procedure and the certainty with which

results from different analyses may be compared. From this discussion, some obvious criteria for standards and intercomparison procedures emerge: detect petroleum over natural background; deter- mine percent recovery and reproducibility; quantitate petroleum fractions and compounds; quantitate

sample loss and contamination.

Recognizing what is required of standards and intercomparison procedures, we may suggest guidelines for obtaining this information: intercomparison with a standard petroleum fraction mixed

with a recently biosynthesized oil; analysis of "standard" particulate matter; internal standards with each sample; blanks with each set of sample

analyses

References

Pierce et al (2) suggested that particulates

provide a means for hydrocarbon transport and in- corporation into the food chain. The analysis of petroleum associated with particulate matter re- quires a more intricate approach than for tar balls, due to the low concentration of petroleum

and the abundance of non-petroleum hydrocarbons.

Often the presence of petroleum may be masked by

the abundance of non-petroleum hydrocarbons.

A useful approach to this problem would be to determine the natural background of hydrocarbons

before petroleum is introduced to the environment.

Baseline surveys are important for areas where

oil drilling and transport may occur in the future.

Instrumentation required for a complete analysis of petroleum is beyond the capability of most laboratories. The asphaltic fraction, which

(1) Farrington, J.W., Teal, J.M., Quinn, J.G., Wade, T. and Burns, K. , Intercalibration of Analysis of Recently Biosynthesized Hydrocarbons and Petroleum Hydrocarbons in Marine

Lipids, Bull. Environ. Contam. Toxicol.,

19(3) , 129-36 (1973).

(2) Pierce, R.H., Jr., Olney, C.E. and Felbeck,

G.T., Jr., pp-'--DDT Adsorption to Suspended

Particulate Matter in Sea Water, Geochim.

Cosmochim. Acta, In Press.

(3) Gruenfeld, M., Identification of Oil Pollutants: A Review of Some Recent Methods , Proceedings of Joint Conference on Prevention

and Control of Oil Spills, March 13-15, 1973,

Washington, D.C., American Petroleum Institute, Washington, D.C. (1973) pp. 179-93.

Key Words: Standards and intercomparison

criteria; Tar balls, Particulate matter; Petroleum analysis. Gas chromatography.

162
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

n-C22 spiked to one subsample of tuna meal to calibrate the FID. Peak areas were measured by the method of peak height x width at one half

height. The unresolved complex mixture area of

the chromatogram was determined by planimetry.

ANALYSES OF HYDROCARBONS IN MARINE ORGANISMS: RESULTS OF IDOE INTERCALIBRATION EXERCISES

1 1 2 J. W. Farrington , J. M. Teal , J. G. Quinn

P. L. Parker^, J. K. Winters-^, T. L. Wade'^

K. Burns^

1. Woods Hole Oceanographic Institution

Woods Hole, Massachusetts 02543

2. Graduate School of Oceanography

University of Rhode Island Kingston, Rhode Island 02881

3. University of Texas Marine Science

Institute at Port Aransas

Port Aransas , Texas

Woods Hole Oceanographic Institution

Contribution Number 3353

Introduction

The importance of intercalibration of hydrocarbon analyses between laboratories was recognized early in the program of baseline

studies of the Office for the International Decade of Ocean Exploration, National Science

Foundation. Three participating laboratories

analyzed a cod liver sample spiked with a distillate cut of South Louisiana crude oil. The

results of this exercise have been published [1].

Four participating laboratories analyzed

a tuna meal sample provided as a working intercalibration sample through the courtesy of the

National Bureau of Standards. The methods of

analysis were not specified. Each laboratory

analyzed the sample using the techniques and methods employed at that time in the respective

laboratories. Our methods of analysis limit

us to hydrocarbons of molecular weights in the range of n-C-,. to n-C^o and as such we refer

only to this range when speaking of "hydrocarbons"

or "total hydrocarbons" in general terms.

Methods of Analysis

The limited space allowed in this presentation permits only a brief outline of the methods of analysis. A more detailed description is available [2, 3].

Laboratories A and D weighed fractions of

the concentrate of column chromatography eluates

on a Cahn el ectrobalance to obtain weights of hydrocarbons in each fraction. Laboratories A,

C and D used an external standard analyzed with

the same instrument conditions as for sample

analysis to calibrate the FID of the gas chromatographs. Laboratory B used an internal standard

Results and Discussion

The concentrations of resolved or partially

resolved peaks, unresolved complex mixture, and total hydrocarbons are given in Table I. The unresolved complex mixture concentration was not a routine measurement in one laboratory and

was not reported from that laboratory.

We think that the agreement between all laboratories for the measurement of the resolved

and partially resolved components is as good

as can be expected considering that no method

of analysis was specified. This is especially

so if one takes into account the fact that squalene was present in the tuna meal sample. The squalene would be only partially recovered

in the hydrocarbon fractions in some chromat- ography operations, while in other cases squalene would be present in two or more fractions from chromatographic separation of hydrocarbons. In addition, squalene is very labile.

We have corrected the values for the resolved peaks by subtracting the concentration

values for squalene. We have assumed in doing

this that the major peak with retention index

similar to that of squalene is in fact squalene. The corrected concentration values are presented

in Table II. The agreement between laboratories

for the resolved or partially resolved component

concentrations is improved. Since squalene is

a major component in most fish and shark liver

samples, the problems we have encountered here

with squalene would also occur in analyzing

fish and shark samples and probably also with

other biological samples.

The agreement between laboratories for

the unresolved complex mixture concentration is fair e.g. compare total of Al + A2; A3; B^ , B^; total of Dl + D2 + D3. The unresolved complex

mixture of hydrocarbons is used as an indication

of petroleum hydrocarbons in some laboratories

for screening samples to detect petroleum hydrocarbons [1 ,4].

The total hydrocarbon concentrations as determined by weighing are also given in Table I. A comparison of the totals obtained by weighing

and the totals obtained by GC analysis show

the former to be higher in all but one case. We think this is the result of the presence

in the tuna meal of hydrocarbons with molecular

weight greater than the 33 carbon n-alkane. These hydrocarbons would be weighed but would

not be measured by the GC analysis employed

because they would not have eluted from the column during the time of analysis. This same phenomena has been observed for the analysis

of sediment samples and for the analysis of some fish tissue and fish liver samples [5].

163
OUTLINE OF METHODS

Laboratory Extraction Method Method of Separation

of Hydrocarbons

Soxhlet extraction with MeOH 48 hours: saponification of lipids for one sub- sample

Reflux extraction with benzene: MeOH (2:1) saponification of lipids

Soxhlet extraction with MeOH followed

by hexane: benzene (9:1): saponification of lipids

Soxhlet extraction with MeOH 24 hours: saponification of lipids

Column chromatography on AI2O3 (5% H2O) over SiO^

(5% H2O)

Thin layer chromatography

on Silica Gel G.

Column chromatography

on Al 20^(6% H2O) over

SiOg (5% HgO)

Column chromatography on AI2O3 (5% H2O) over

Si02 (5% H2O)

Gas chromatographic analyses were as follows:

Laboratory Column Temperature Program

a. 2.34 m X 3.2 mm

o.d. 3% ApL on Chrom.

W 80/100

b. 3.1 m X 3.2 mm o.d. 12% FFAP on Chrom. W 80/100

1.8 m X 3.2 mm o.d. 3% ApL on Chrom. W 80/100

a. 2.13 m x 3.2 mm o.d.

S% FFAP on Gas Chrom. Q

b. ApL SCOT column 45.7 m

2.34 m X 3.2 mm o.d. 37c ApL on Chrom. W 80/100

80° to 290°C at 6°/min.:

held at 290°C until n-C

28 eluted

125° to 270°C at 4°/min.:

held at 270°C until n-C eluted

28

150° to 280«'C at eVmin.;

28 held at 280°C until n-C eluted

100° to 285° at 6°/min.

120°Cto 225°C at 4°/min.

80° to 290°C at 6°/min. held at 290°C until n-Cgg eluted

A comparison of the reported relative

abundance of n-alkanes to pristane for the four laboratories is given in Table III. The agree- ment is fair overall with a few discrepancies.

It is interesting to note that the discrepancies

are not always from the same laboratory. The result for the analysis of the n-alkanes are some- what disappointing given the agreement for pris- tane concentrations in cod liver oil which was analyzed by three laboratories!!]. The concen- tration values for the pristane in tuna meal

are given in Table IV. The agreement for pris- tane at the 1 to 10 pg/g dry weight level is not as good as that achieved for the cod liver sample at the 200 to 300 ug/g lipid concen- tration level for pristane. We estimate

on the basis of lipid analysis that tuna

meal contains 15 to 50 ug pristane/g lipid. The precision for the tuna meal pristane

concentration is +64% relative standard deviation compared to the precision of ±2%

r.s.d. for the pristane in the cod liver oil.

164
Table I. Hydrocarbons in Tuna Meal [yg/q dry weight)

Al A2 Total A3

1 h

C Dl D2 D3 Total

Resolved Peaks 8.5 23.0 31.5 12 18.0 20.2 26.0 7.5 NA 50.0 57.5

Unresolved Complex

Mixture

39.0 10.0 49.0 41 29.5 35.2 ND 39.7 NA NP 39.7

Total (g.c.) 47.5 33.0 80.5 53 47.5 55.4 47.2 NA 50.0 97.2

Total (weighing) 106.0 76.5 182.0 140 NA NA 57.2 13.6 50.0 120.5

Laboratory A - Column Chromatography -

Al : 2 column volumes of pentane; A2: 2 column volumes benzene; A3: 3 columns of 5% benzene in pentane.

Laboratory B - B, , Bp duplicate analyses TLC procedure.

Laboratory C - cil urn Chromatography - 1 column volume hexane. Laboratory D - Column Chromatography - Dl : 1 column volume pentane; D2: 1 column volume 10% benzene in pentane; 03: 1 column

volume 20% benzene in pentane.

NA - Not analyzed

NP - Not present

Table II. Hydrocarbons in Tuna Meal Corrected by Deduction of Squalene Concentration (yg/g dry weight)

Al A2 Total A3 ^1 ^2 C Dl D2 D3 Total

Resolved Peaks 8.5 10.4 18.9 8.5 12.4 13.1 26.0 7.5 NA 13.8 21.3

Unresolved Mixture 39.0 10.0 49.0 41.0 29.5 35.2 NA 39.7 NA NP 39.7

Total 47.5 20.4 67.9 49.5 41.9 48.3 47.2 13.6 13.8 74.6

NA - Not analyzed

NP - Not present

Table III. Abundance of n-Alkanes Relative to Pristane

n-Alkane A-1 A-3 B C D

15 0.81 0.85 N.R. 0.66 0.67

16 0.12 0.09 0.40 0.13 0.04

17 0.40 0.42 0.40 0.39 0.44

18 0.17 0.17 0.17 0.09 0.14

19 0.17 0.15 0.17 0.20 0.03

20 0.13 0.11 0.10 N.R. 0.05

21 0.17 0.14 0.14 0.06 0.17

22 0.12 0.45 0.27 N.R. 0.04

23 0.13 T N.R. N.R. 0.16

24 0.13 T N.R. 0.01 0.04

25 0.07 N.R. N.R. N.R. 0.03

26 0.11 N.R. 0.40 N.R. 0.06

27 0.12 N.R. N.R. 0.07 0.05

28 0.12 N.R. N.R. N.R. N.R.

NR - Not reported

T - Trace

Table IV. Pristane Concentration in Tuna Meal (pg/g dry weight)

Al A3 B C D_

1.9 2.0 3.0 5.7 2.0

165
We believe that the latter value is fortuitous

and does not reflect the true precision of the analysis since the best precision one would

expect for measurement of the GC peak for pristane is about ±5% r.s.d.

The results we report here are only a start

at intercal ibration of analyses for hydrocarbons

in marine tissue samples. The need for intercalibration of much more sophisticated techniques

such as GC-mass spectrometry and compound type

analyses by mass spectrometer-computer systems

is already apparent as these techniques are now

being used for analysis of hydrocarbons isolated

from marine samples.

There has been an increase during the last few years in the number of laboratories analyzing

marine samples for hydrocarbons and attempting

to determine petroleum hydrocarbons in the presence of recently biosynthesized hydrocarbons.

Our experience reported here and elsewhere, [1]

points to the need for i ntercal ibration. Our laboratories now have a basis for comparing

results of analyses of marine tissue samples.

We think it is absolutely essential that intercalibration be expended to include more labor- atories, more analytical methods and different

types of samples. We also think that there is an obvious need for intercalibrations where

the same methods of analysis are used.

References

[1] Farrington, J. W. , Teal, J. M., Quinn,

J. G., Wade, T. , and Burns, K. , Bull . of

Environ. Cont. and Tox . 10: 129-136 (1973).

[2] Quinn, J. G. , and Wade, T. L., Marine Mem- orandum Series No. 33, University of Rhode

I-land (1974).

[3] "Baseline Studies of Pollutants in the Marine Environment", Background papers for

a Workshop, sponsored by the National Science Foundation, Office for the International Decade of Ocean Exploration, Brookhaven National Laboratory, May 24-26,

1972, 555-676.

[4] Farrington, J. W. , Tech. Report No. 73-57, Woods Hole Oceanographic Institution, Woods

Hole, Massachusetts (1973) (unpublished

manuscript)

.

[5] Farrington, J. W. , Unpublished results.

Key Words: Hydrocarbons in Marine Organisms;

Intercal ibration; Oil Pollution.

Acknowl edgements

This work was supported by Grants GX-28334,

GX-35212, GX-28340, and GX-30108 from the Office

for the International Decade of Ocean Exploration, National Science Foundation, and Grant

R 802724 Environmental Protection Agency.

166
DBS Spec. Publ. A09, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithers- burg, Maryland. May 13-17, 1974 (Issued December 1974).

IDOE-5 INTERCALIBRATION SAMPLE: RESULTS OF ANALYSIS AFTER

SIXTEEN MONTHS STORAGE

G. C. Medeiros and J. W. Fam'i.qton

Chemistry Department

Woods Hole Oceanographic Institution

Woods Hole, Massachusetts 02543

Woods Hole Oceanographic Institution

Contribution Number 3346

Introduction

The advent of growing scientific and govern

mental interest in marine oil pollution has heightened the need to intercalibrate the

various analytical techniques employed in oil pollution study. Laboratories engaged in the quantification of petroleum hydrocarbons

require intercalibration to facilitate comparison of data and to assess the precision and accuracy of their methods of analysis. For

initial intercalibration efforts of this type,

chemically stable, petroleum-spiked samples

are needed.

We participated with two other laboratories in an intercalibration exercise in 1972

(1 ) using as an intercalibration sample a cod liver lipid extract spiked with a distillate

cut of South Louisiana crude oil. In order

to test the stability of this sample, we withdrew two subsamples and stored them separately

from the bulk mixture. We have analyzed these subsamples sixteen months later using the techniques detailed below. These techniques

are slightly modified from the original tech- niques employed by our laboratory in the earlier study (1). The gas chromatography (GC) screening procedure and its application to the study of petroleum pollution in marine samples

have been discussed elsewhere (1, 2, 3).

Experimental

Methods of Analysis

In February, 1974, lipid concentrations of

each subsample were determined and aliquots

containing about 120 mg of lipid were saponified

under reflux for twenty-four hours in 0.3 N KOH

in 3:1 methanol :water solution. Non-saponif iable

lipids were partitioned from the aqueous methanol solution into pentane, and the pentane extracts were dried by standing at least two hours over

Naj,SO/i. The extracts were evaporated to dryness

ana the resulting residues were weighed.

Residues were dissolved in 1 ml of pentane

and charged to columns of 4 g alumina (5% water)

packed over 4 g silica (5% water). The columns were eluted with one column volume each of pentane, 10% benzene in pentane, 20% benzene

in pentane, and benzene. The second and third eluates were combined for subsequent analysis.

Quantification of hydrocarbons was accom- plished by the following GC method. Chromatograms of the first eluate and the combined second

and third eluates were obtained on a 5 ft.

X 1/8 in. OV 101 on 100/120 mesh H/P Chromo- sorb column. The column was operated with a He carrier gas flow rate of 10 to 15 ml/min., and temperature was programmed from 70 to 270°C at

6°C per minute. The instrument employed was a Varian 1400 GC equipped with a flame ionization

detector. The detector signal was routinely

calibrated for sample experimental conditions

by obtaining a chromatogram of a standard

mixture of n-alkanes n-C-,- to n-Cpo (even carbon

numbers). Peak areas on sample ana standard

chromatograms were calculated using peak height

times peak width at half height. The unresolved

complex mixture area in the sample chromatograms

was determined by planimetry. The integrated

area of the unresolved complex mixture and the

peaks other than pristane is used as the estimate

of petroleum hydrocarbons in the sample (1, 3).

Results and Discussion

The results of our recent analyses and the average values obtained 18 months earlier are presented in Table I. They are in agreement

Table I. pg Hydrocarbons /g Cod Liver Lipid.

Ave. Value 8/16/72 10/22/72

± s.d.(1972)

Preparation of IDOE-5 Intercalibration Sample

A cod liver lipid extract was spiked with

371.8 yg of a distillate cut (n-C,, to n-C^g) of South Louisiana crude oil per gram of iTpid

in January, 1972. The sample was stored under

at 0°C in the dark in a glass bottle with a Teflon lined cap. The subsamples were withdrawn

from the bulk mixture on August 16, 1972 and October 22, 1972 after warming the mixture to room temperature and allowing the lipids precipitated from the sample at 0°C to go into solution.

The subsamples and the main sample were then flushed with nitrogen and stored at 0°C in the dark in glass bottles or vials with Teflon liners.

Peaks and Complex

Mixture 406 ± 26 yg/g 455 yg/g 426 yg/g

(pet.hyd.)

Peaks 79.2 ± 10.5

Complex 326.8 ± 27.7 Mixture

Pristane 270.4 ± 5.2

71

384

267

59

367

270

This is used as the estimate of petroleum hydro- carbons and includes peaks other than pristane.

167
within inter laboratory and intra! aboratory

precision for this type of analysis. Figure 1 contains chromatograms of (1) the distillate

cut, (2) pentane-eluted hydrocarbons in unspiked

cod liver lipids, (3) pentane-eluted hydrocarbons

in the original intercalibration exercise and,

Figure 1

Gas chromatograms of hydrocarbons in pentane

eluate of column chromatography.

AA - Automatic attenuation of detector signal UCM - Unresolved complex mixture

Pr - Pristane

Ph - Phytane

Numbers - n-alkanes

I - Chromatogram obtained in original intercalibration on 3% Apiezon L. column.

II- Chromatogram obtained in recent analyses

on 1.5% OV-101 column.

(4) pentane-eluted hydrocarbons in our recent

analyses. The chromatograms from the original

exercise were obtained on a 7.5 ft. 1/8 in. Apiezon L column. Although the two IDOE-5

chrc natograms shown in Figure 1 were obtained

on two different GC columns, the results are comparable for the purposes of this type of analysis.

The major portion of the petroleum distillate

cut spiked into the cod liver lipid elutes from column chromatography in the first fraction

(pentane eluate). A small portion elutes in the second fraction (10 and 20% benzene) and none is detected in the third fraction (benzene

eluate). This is not to be expected for all

crude oils, fuel oils or other petroleum pro- ducts and should be considered characteristic

only for this distillate cut. A comparison of

the unresolved complex mixture values for Fractions I and II and the values for the analysis of the petroleum distillate cut by column chromatography are given in Table II.

Table II. Hydrocarbons from Petroleum Distillate Cut in Column

Chromatography Fractions.

IDOE-5 S.Louisiana

8/16/72 10/22/72 Crude Distillate

Cut

Fraction I 90% 85% 85%

Fraction II 10% 15% 15%

The comparison shows that the values are in general agreement although the data is insuf- ficient at this time to provide an estimate

of the precision for the column chromatography

separations for Fractions I and II.

Fraction II also contains squalene from the cod liver lipids. Values for squalene are not presented here because the lability of this compound renders it difficult to analyze quan- titatively under the conditions we have employed

for these analyses.

We have found that some lipid material

precipitates out of hexane solution upon stor- age at 0°C. We were concerned that we would

encounter problems in regaining a homogeneous

mixture upon warming to room temperature. In the process of subsampling IDOE-5 for our own

use and for the use of other laboratories we

have cycled the extract from 0°C to 25°C to 0°C

a number of times. Each time we have found

that vigorous shaking after equilibration at

25°C is sufficient to obtain a sample which is homogeneous to inspection. Furthermore, the recent results reported in this paper demon- strate that chemical homogeneity has been maintained, at least with respect to hydrocarbons.

These results clearly demonstrate that it

is feasible to prepare and store lipid extracts

of this type for at least sixteen months. This

is also of interest from the point of view of baseline studies and monitoring of areas where

petroleum pollution may occur, e.g. offshore

drilling or refinery locations. Economic

feasibility may dictate that all samples obtained cannot be analyzed for hydrocarbons to detect

petroleum pollution. However, it may prove

feasible at least to extract the samples and store the lipid extracts. A few key samples

from selected sampling stations could then be analyzed for hydrocarbons to determine whether

petroleum pollution is present. If the key

168
samples analyzed for a given time period indicate

the onset of petroleum pollution or pollution

on the increase, then all the samples from that

given set could be analyzed to determine the extent and severity of the pollution. The

results reported here indicate that it would

be feasible to store lipid extracts for later hydrocarbon analysis.

Another facet of this work deserves mention.

These analyses were performed satisfactorily by

a college freshman under the direction of the

authors. This demonstrates that the wet chemical

and Instrumental analyses required can be accom- plished by a trained laboratory assistant supervised by professional scientists. We ask that

all laboratories which have requested and re- ceived IDOE-5 subsamples report their results so that we may have a larger data base for statistical calculations.

We recognize that other methods and techniques

have been, and will be employed in analysis of marine samples for petroleum pollution. Some are more sophisticated than the methods described

here. However, more detailed intercalibration

of all methods used in petroleum pollution

studies is needed if we are to compare results obtained in different laboratories using various

methods of analysis.

Science Foundation and from the Office of Naval Research Contract N00014-66-C0 241; NR083-004

are gratefully acknowledged.

We wish to express particular thanks to

E. Arthur Robinson, Jr., who performed the analyses reported in this paper and Drs. Werner

Deuser and Oliver Zafiriou for their comments.

References

[1] Farrington, J. W., Teal, J. M., Quinn,

J. G., Wade, T., and Burns, K., Inter- calibration of Analyses of Recently Biosynthesized Hydrocarbons and Petroleum

Hydrocarbons in Marine Lipids, Bull . of

Environ. Cont. and Tox . ]£, 129-136 (1973).

[2] Blumer, M., Blokker, P. C, Cowell, E. B.

,

and Duckworth, D. F. , Petroleum, in A Guide to Marine Pollution , Goldberg, E. D. Ed., Chapter 2, Gordon and Breach Science

Publishers, Inc. (1972).

[3] Farrington, J. W. , Analytical Techniques

for the Determination of Petroleum

Contamination in Marine Organisms , Woods

Hole Oceanographic Institution Technical

Report 73-57.

Acknowledgements:

This work was supported principally by the

U.S. Environmental Protection Agency, Grant R-802724 and the Office for the International

Decade of Ocean Exploration, National Science Key Words: Gas chromatography, hydrocarbons,

Foundation Grant GX-'35212. This funding and intercalibration, marine organisms, petroleum

additional funding from Grant GA-19472 National pollution.

169
I
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

USE OF LOW MOLECULAR-WEIGHT-HYDROCARBON

CONCENTRATIONS AS INDICATORS OF MARINE

POLLUTION

William M. Sackett and James M. Brooks

Department of Oceanography

Texas ASM University

College Station, TX 77843 U.S.A.

Dissolved low-molecular-weight

hydrocarbon concentrations in surface

water have been determined for several

thousand miles of cruise tracks of the

Texas ASM University ships, R/V Alaminos

and R/V Gyre, in the Gulf of Mexico for

the period from 1971 to the present.

The hydrocarbon sniffer system and some

of the results are reported in papers by

Brooks [1,2] and Sackett [3]. The data

generally indicate that the most important sources of Ci through C5 hydrocarbons are related to man's activities.

These sources include ports and estuaries

with their associated shipping and petrochemical activities, offshore drilling

and production platforms , and ships which

discharge oily ballast water and/or

clean their fuel tanks at sea. The water

column several miles distant from at least one example of each of the three

types of sources showed several orders

of magnitude higher concentrations than

observed for the open Gulf. Natural

seeps are also significant sources of

hydrocarbons in the Gulf but the magnitude of their contribution relative to man's is probably very small.

On a recent cruise in March of 1974

»

we surveyed the water in and around

several groups of platforms offshore

Louisiana. The groups farthest out,

presumably the newest, showed C1-C5

dissolved hydrocarbon concentrations in

nearby waters generally two to three

orders of magnitude higher than concen- trations in surface water of the open

Gulf of Mexico , where the latter are equilibrium concentrations determined by

the partial pressures of the various

gases in the atmosphere. Surface water

around platforms nearer to the coast,

presumably in place for a longer period

of time than the platforms cited above,

had much lower levels but still one to two orders of magnitude higher than open

Gulf surface water.

Figure 1 shows the distribution of

relative ethane concentrations (where the

total open ocean surface values of C2 hydrocarbons are set equal to one) around

a group of platforms at 2 8° 5

8

' N, 9 2° 0

0

' W

.

All saturated C2 to C5 hydrocarbons,

which are certainly petrogenic, as well as methane which may also be formed biochemically show approximately the same relative concentrations. The highest values,

85,000 times open ocean values or about

0.3 ml of ethane per liter of sea water, were found near what appeared to be an underwater "flare." This phenomenon, a large volume of gas bubbling to the sur- face at one spot, next to one platform,

covered an area of about 100 square feet.

High hydrocarbon levels , apparently from

this one source, were observed in the

surface water over an area greater than

25 square miles.

A very recent paper by Swinnerton

[4] reports that approximately 90% of

the dissolved C2 hydrocarbons found in

surface open ocean water is actually

ethylene of biogenic origin. As our "sniffer" mode of operation does not

differentiate between ethane and ethylene, the relative values for ethane and

propane previously reported by Brooks

[1,2] and Sackett [3] and shown in

Figure 1 are minimal and the actual

values may be an order of magnitude

higher in many instances.

Three years of surveying and thousands of analyses cor.fi rm the popular

sentiment that offshore petroleum production and tanker operations are con- taminating much of the Gulf of Mexico

coastal waters with petroleum derived

low-molecular-weight hydrocarbons. This

seemingly contradicts the conclusions of

Koons and Monaghari [5] who state:

"It is important to note that the

C1-C2 values do not increase significantly with close proximity to

the platforms .... Producing operations

are not changing the hydrocarbon

content of nearby water."

It should be pointed out that their study

included only a few analyses in the

vicinity of South Timbalier Block 54 Field at just one particular time. No

doubt, each field has its own set of

pipelining, flaring, waste discharging,

and other operational characteristics

which determine the amounts of lowmolecular-weight hydrocarbons being

introduced into the surrounding water

column. The magnitude of these inputs

in the vicinity of any given platform

presumably is not constant but changes

with age and depletion of the field,

weather, nearby production activities,

leaks and breaks, etc. so that a few

samples at a few sites may not provide

a true measure of the annual discharge

by such operations.

On the basis of our experimental

data on the effects of low-molecularweight hydrocarbons on primary producers,

the biological effects of even the

extremely high concentration levels

171
Figure 1. Relative ethane concentrations (1 = 3x10 ml of dissolved ethane at S.T.P. per liter of sea water) at 28°58'N, 92°00'W. Solid squares are locations of

platforms; solid circles are exposed well heads.

observed around the group of platforms

pictured in Figure 1 are probably negligible. However, in most instances,

these comounds, which may be detected

with great sensitivity are indicators

of the presence of the more difficult

to measure, relatively soluble, highly

toxic components of petroleum such as the aromatics and various nitrogen,

sulfur and oxygen containing compounds.

One exception to this generalization is an introduction from an operation producing dry natural gas containing very

little C3 and higher-molecular-weight

constituents

•

In summary, large areas of coastal

water offshore Texas and Louisiana have

up to six orders of magnitude higher

concentrations of low-molecular-weight

hydrocarbons than open ocean surface

water. These high levels are most cer- tainly petroleum-derived and due to offshore petroleum production operations.

The observed high levels of Ci to C3 hydrocarbons do not seem to be detrimental to marine life, but nevertheless

serve as sensitive indicators of the more

toxic components of petroleum which

usually are being simultaneously introduced to the ocean. Acknowledgement

:

Financial support for this study was provided by NSF Grant No. GX-3734U.

References

:

[1] Brooks, J. M. , Fredericks, A. D.

,

Sackett, W. M. and Swinnerton, J. W,,

Baseline Concentration of Light

Hydrocarbons in Gulf of Mexico,

Environ. Sci. £ Technol. 1_, 639-H2

(1973)

.

[2] Brooks, J. M. and Sackett, W. M.,

Sources, Sinks and Concentrations of

Light Hydrocarbons in the Gulf of

Mexico, J. Geophys. Res. 78 , 5248-58

(1973)

.

172
[3] Sackett , W. M. , Significance of Low

Molecular Weight Hydrocarbons in

Eastern Gulf Waters, Proceedings of

Marine Environmental Implications of

Offshore Drilling Eastern Gulf of

Mexico: 1974, January 31 to February

2, 1974, St. Petersburg, Florida

(1974) 455 pp.

[5] Koons, C. B. and Monaghan, P. H.,

Petroleum Derived Hydrocarbons in

Gulf of Mexico Waters, Trans . Gulf

Coast Assoc. Geol. Soc.Ts", 170-81

(1973)

[4] Swinnerton, J. W. and Lamontagne , R. A. , Oceanic Distribution of LowMolecular-Weight Hydrocarbons:

Baseline Measurements, Environ. Sci.

8 Technol. (In Press).

Key Words: Biological effects; Gulf of

Mexico; hydrocarbon "sniffer"; lowmolecular-weight hydrocarbons; marine

pollution; pollution indicators;

petroleum production platforms.

173

NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

FLUORESCENCE MONITORING STODY AT OCEAN WEATHER STATION "P"

W.J. Cretney and C.S. Vfong

Ocean Chemistry Division

Marine Sciences Directorate, Pacific Region

Departinent of the Environm^-nt 211 Harbo^ir Road

Victoria, B.C. V9A 3S2 Canada

In August and Septenber of 1373 on

Cruise 73-006 of the weathership, Quadra, a

fl\X5rescence i;;onitoring study of seawater was

carried out at Station "P" and along Line "P"

(fig. 1) usi'ig a technique patterned after that

of Levy [1] :nd Gordon [2]. Sanples of seawater

150" Iter 130* 120"

i

Kfl ;

i

1

i % ]

i

Kx-^"-"""

j PACIFIC OCEAN

150' I40" 1.

1

^

( !

0- 120-

Figure 1. Chart showing Ocean Weather

Station "P" and Line "P" positions.

were obtained frcm the bow of the ship while

it was proceeding at about 5 knots using a

solvent washed 5 gallon stainless steel bucket

and a nylon rope. A subsairple of seawater of

slightly more than 3 1 was poured into a hydrocarbon free, one gallon glass bottle containing

60 wg of mercuric chloride. The bottle was

sealed with a plastic cap having a teflon

liner and stored in the ship's freezer. Another subsairple of 1.5 1 was extracted

with two consecutive portions (65 ml and

25 ml) of methylene chloride. The canbined

extracts were placed on a hot water bath at

55° to 60°C and the solvent evaporated. The

residue was taken in 15 ml of cyclohexane

and the fluorescent intensity at 383 nm was

determined for an excitation wavelength of

308 nm. The fluorescent intensity was corrected

for background contributions fron the cyclohexane

and the residual fluorescence of irrpurities in

the methylene chloride and ccin:pai-e<3 with stan- dards of chrysene of similar concei trations.

Following the cruise of the Quadra, the

preserved seawater sairples were analyzed in the

land-based laboratory in the same manner with

the exception that a rotary evaporator was used

to ranove the solvent. The concentration of

fluorescent ccrtpounds in chrysene equivalents

as determined on shipboard and in the land-based

labDratory are given in table I. The mean values

Table I. Concentration in Chrysene

Equivalents of Fluorescent

Compounds on Line "P" and

Station "P."

Station

2

5

6

712

P

P

P

P

PP

P

P

P

P

P

P

12

10

9

7

4

3

21

Date

(1973)

Aug. 4 Aug. 4 Aug. 4 Aug. 4 Aug. 6

Lab. Anal.

Cone. (ppb)

0.069

Aug. 8

Aug. 11 Aug. 14 Aug. 17 Aug. 20 Aug. 23 Aug. 26 Aug. 29

Sept. 1 Sept. 4 Sept. 7 Sept. 12 Sept. 15 Sept. 16 Sept. 17 Sept. 17 Sept. 18 Sept. 18 Sept. 18 Sept. 19 Sept. 19

0.071

0.035

0.030

0.028 0.027

0.060

0.032

0.018

0.017

0.013 0.012

0.025

Ship Anal.

Cone, (ppb)

0.017 0.035

0.038 0.019

0.024^

0.08 0.11°

0.48 0.019

0.031

0.054 0.040

0.039

0.027 0.015

0.031 0.031

0.034

0.045

020

028

023 015

043

018

092 082

^sanples were preserved with mercuric chloride

(ca, 60 mg/gal) . samples were worked up

iranediately without the addition of preservative. ° duplicate determinations on same sea- water sanple.

for Station "P" seawater determined in the

laboratory and on the ship were 0.031 ppb and

0.039 ppb, respectively with standard deviations

of 0.018 and 0.020 ppb, respectively. The mean

difference in paired values was 0.008 ± 0.007 ppb with a 90% confidence of the actual differ^

ence being within the range indicated [3]. By

the same token, however, there is only about a

50% chance of there being an actual loss of

13%-28% (0.008 ± 0.003 ppb) in the original

fluorescent intensity on storage for about two

months. Although the results strongly suggest

that there was a loss of fluorescent intensity on storage, there is insufficient precision

and data to attach much significance to the mean difference between the shipboard and land- based laboratory results. Notwithstanding a

loss of fluorescence on storage, the laboratory

175
results, vMch were obtained under scn:?3ulously

hydrocarbon-free conditions, confirm the lew

level of fluorescent coipounds detected by

shipboard analysis of seavater at Station "P" and along Line "P." The average value of

0.039 ppb, for Station "P" seawater, if con- verted fron chrysene equivalents to equivalents

of a typical Bunker C oil, would correspond to about 0.2 ppb. This value is about an order

of magnitude smaller than the least amount

vAuch, it is claimed [2], might be confidently

attributed to petroleum pollution.

Chrysene was chosen as an analytical

standard for residual or weathered crude oils

after consideration of over three dozen

different ccrrpounds. Among considerations

taken in this choice was the knowledge that

the oils of interest in general exhibit a

excitation maximum in the regicai 290 nm to

330 m and an endssion maximum in the region

360 m to 400 nm as indicated by a number of

saitples studied in our laboratory as well as other laboratories [1, 2, 4, 5]. A further

consideration was that a suitable standard

should be obtainable at low cost and in high

purity, particularly with regard to fluorescent

impurities. As shown in figure 2, chrysene

exhibits maxima in the desired range in both

its emission and excitation spectra. Chrysene

can be obtained in better than 99% claimed

purity for about 10 cents a gram. Further, our sartple of chrysene chronatographed on

silica gel as a single carpound for the

purpose required as shewn by fluorescence.

a b

n

COn

z

. ; 1 1 1

± 1

' 400 350 350 300 250 WAVELENGTH (nm)

Figure 2. a. Elnission spectrum of chrysene

with exciter at 308 nm. b. Excitation spectrvm

of chrysene with analyzer at 383 nm.

ultraviolet and refractive index monitoring of

the column effluent. The chromatographic

behavior supported the claimed purity in the case of chrysene, but did not in the case of

seme other ccirpounds vAuch otherwise were

good candidates for the standard.

Although there are certainly other suitable

standards, we feel that chrysene best fits the

criteria as seen by ourselves. At any rate we

strongly favor the choice of a siiigle conpound, or perhaps a mixture of a few certpounds, as a

standard since such a choice vrould mean that

the standard would be readily available to

researchers through chemical sv^iply houses

obviating a large controlled sv;5jply as would

be necessary in the case of an oil as standard.

Following the laboratory analysis of

Station "P" and Line "P" seawater, the sanples were stored at 5°C for an additional six ironths. By this time, following Zsolnay's lead [6,7], a oembined High Speed Liquid ChraiHtogr^hy-Fluorsescene Spectrosccpy (HSLC-FS) method was being

used routinely for the analysis of seawater. A

Waters Associates model 202/401 liquid chrematograph was interfaced with a Perkin-Elmer model

204 fluorescence spectrpphotcraeter by means of

a flow-through cell (0.1 ml internal volume).

A 150 ran X 1.8 rm column packed by the balanced

density method [8] with 5 y silica gel

(LiChrosorb Si-60, E. Merck Co) was used with a

flew of hexane at a rate of 0.5 ml/hin. The

exciter and analyzer settings on the fluorescence

spectrophotcmeter were 308 nm and 383 nm, respectively. Under these conditions the center of the chrysene band passed into the fluorometer

cell in about 6.5 min as shown in figure 3c. The seawater sanples frcm Line "P" and Station

"P", some of vAiich had been oembined prior to

storage to give sufficient quantities for

analysis, were extracted as before. The extract,

however, was ultimately taken v;^? in 0.5 ml of

hexane instead of 15 ml of cyclohexane and a

0.05 ml portion injected on the column. The

results of two such injections for different

sanples are shown in figures 3a and 3b and can be ccTTvared with the result of an on column

injection of 830 pg (in 0.05 ml of hexan^ of

chrysene at the same instrument sensitivity.

A second extraction was performed on each

sanple of seawater to check on the efficiency

of the first extraction and as an additional

check on the solvent purily and cleanliness

of equipment. If any fluorescent ccnpounds were extracted in the second extraction, their

contribution was added to the contribution of

the first extraction. Blanks were run on

each new batch of solvent or v*ienever there was an indication of contamination and a

blank correction applied to each sample run. The area urider each curve was determined with

the aid of a Disc integrator and converted

into equivalents of chrysene. Chrysene

standards fjere run periodically as a check on

the sensitivity of the instrument.

The result of the HSLC-FS analysis are

given in table II. The average value in

chrysene equivalents for the Station "P" samples was 0.016 ppb with a standard deviation

176
Figure 3. a. chxanatogram of the extract of

the seawater saitple of Sept. 7 . b. chranat- ogram of the extract of the catibined seawater

sanples of Aug. 14 and Aug. 17. c. chronatogram

of 0.83 ng of chrysene.

Table II.

Cruise Station

Concentration in Chrysene Equivalents

of Fluorescent Ccnpounds on Line "P" and Station "P" as determined by

Combined High Speed Liquid Chronatography^Flvorescence Spectroscopy. Date

(1973) Concentration (ppb)

73-006

73-006

73-006

73-006

73-006

73-006

73-006

73-009

73-009

Aug. 4 , Aug. 14,17°

Aug. 20 . S^. 12*^ Aug. 29, . Sept. 1,4°

Sept. 7 Sept. 17

Sept. 18

Dec. 14 Dec. 30

0.026^

0.019

0.014

0.018 0.011

0.027 0.025°

0.012 0.010°

0.013

0.018

^ A liter sanple was extracted. ^The samples

ta}cen on these dates were ccnibined to provide

enough seawater for analysis. ° Di^licate

determination on same seawater sample.

of 0.0033 ppb. The standard deviation was

considerably smaller than in the previous

determinations. This result may be a reflection

of increased operator e:q)erience in extracting

the seavater sanples or of an inherently better

precision in the method. The average valvie is

close to one-half that determined for the

Station "P" sanples in the previous laboratory

analysis. This is also true if the subset of

sanples vMch were analyzed on both occasions is

considered. The further reduction of fl\K)rescent

intensity of the seawater extractables indicates

either a further loss of fluorescent ccmpounds on extended storage or the inpeding of the passage of polar fractions of fluorescent ccnpounds

throiagh the silica gel column. That the latter

possibility may be true, to seme extent, is

indicated by the appearance of very broad

flixjrescent bands fron the column after heavy use

for a few weeks. Acetonitrile, methylene

chloride and carbon tetrachloride provide a convenient elution series for cleaning the

column.

This initial fluorescent monitoring study, we feel, provides a reliable indication of the

level of fluorescent coipounds in oceanic water

off the Canadian West Coast against vAiich any

increases attributable to future vessel traffic on the coast can hopefully be measured.

Additional studies to supplement those in this

report are anticipated to provide a nore extensive baseline and determine, if possible, the

origin of the ccnpounds measured. We believe

that the HSLC-FS method is more useful than the original fluorescence method since it has the

capability of providing more information with

the same input of work. In the study herein

described, nevertheless, the two methods

definitely gave cotparable results and an

exacting intercalibration of the methods is cer- tainly warranted.

References

[1] Levy, E.M., Water Res. 5, 723-733 (1971).

[2] Keizer, P.D. and Gordon Jr., D.C., J. Fish

Res. Board Can. 30, 1039-1046 (197371

[3] Bennett, C.A. and Franklin, N.L., Statistical Analysis in Chemistry and the Chemical

Industry, John Wiley & Sons, Inc., New York

(1954).

Zitko, v.. Bull. Environ. Contam. Toxicol.

5, 559-564 (1970)

.

Coakley, W.A. , Coiparative Identification

[4]

[5] of Oil Spills by Fluorescence spectroscopy

Fingerprinting, in Proceedings of Joint

Conference on Prevention and Control of

on Spills, American Petroleum Institute,

Washington (1973).

[6] Zsolnay, A., Marine Chan. 1, 127-136

(1972-73)

.

[7] Zsolnay, A., Chgnosphere, 253-260 (1973)

[8] Majors, R.E., Anal. Chem. 44, 1722-26

(1972).

Key words: Fluorescent monitoring. Pacific

North East; chrysene standard; combined High

Speed Liquid Chrcmatography-Fluorescence

Spectroscopy.

177

TOPICAL SESSION IV.

Oil in Marine Organisms and Sediments: Sampling and

Analytical Methods

179
I
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

SAMPLING MARINE ORGANISMS AND

SEDIMENTS FOR HIGH PRECISION GAS

CHROMATOGRAPHIC ANALYSIS OF

AROMATIC HYDROCARBONS

Herbert E. Bruce

National Marine Fisheries Service

Auke Bay Fisheries Laboratory

Auke Bay, Alaska 99821 U.S.A.

and

Stuart P. Cram

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234 U.S.A.

Sampling techniques for the collection of sediment samples and inner tidal

organisms have been developed as part of

a hydrocarbon baseline study in Prince

William Sound Alaska. All of the samples were collected during low tides and therefore only hand collection methods have

been considered. The sample collection

experiments were designed to reflect sea- sonal, species, and geographic variations

during a one year period and to be com- plimentary to a continuing biological

baseline study in the same area. Sample collection for baseline studies in the sub-part per billion to part

per million concentration range from pristine environments, such as Prince William

Sound, requires that every possible precaution be taken to minimize contamination

and sample handling errors. At these

ultra-low concentrations, it is imperative

that a creditable sampling program be designed in order to obtain meaningful re- sults and because the high cost per sample

limits the number of samples which can be

analyzed. At the same time, samples must

be statistically representative, collected

in a reproducible manner, and taken in

such a manner as to not perturb the species

population and distribution.

New wide mouth glass jars were cleaned in the laboratory prior to use by the

following sequence:

(1) Soap and water wash,

(2) Multiple distilled water rinses,

(3) Acid wash in concentrated H-SO.

for >^ 5 min. , (4) Eight (8) rinses in distilled

water,

(5) Two (2) rinses with hydrocarbonfree water,

(6) Rinse with singly distilled

methanol (from reagent grade)

(7) Two rinses with doubly distilled n-pentane (from reagent grade)

and

(8) Flushed with N2 vapor taken

directly from a LN2 source. The organic free water was prepared by re- distilling distilled water over KMnO.-KOH

and pumping through a 90 cm by 2.5 cm preparative scale liquid chromatography

column. The column was packed with XAD-2

resin which was previously cleaned by

Soxhlet extraction with acetonitrile for

24 hours and methanol for 48 hours. The

purpose of the N, flushing before sealing

was to provide a bacteria- free , inert

atmosphere. Aluminum bottle cap liners were used to make an air-tight seal in

the bottles. The liners were cleaned in

a sonic cleaner with acetone and pentane,

successively.

Polyethylene gloves were used by all

personnel in order to avoid contamination

by body oils. Although rubberized rain

gear was generally required, all samples were collected with all personnel, boats,

and other craft located such that the tidal wash was away from the sample. Access

to the sample sites was by float-plane,

cruiser, or ship. In all cases these

craft and shuttle skiffs to shore were well

removed from the sample site. This minimized contamination of the samples from

residual oils and hydrocarbons from the

boats. In addition, wading boots were cleaned by wading long distances in the

mud and water.

Sediment samples were collected from

mudflats, glacial or other fresh water

outflows, rocky inner-tidal flats, sandy

inner- tidal flats, and from a remote con- trol site. Sampling was effected by

taking two vertical cuts for each sample

with a Plexiglas right circular cylinder

5 cm. i.d. by 8.8 cm. long and trimming

the excess sediment with a clean stainless

steel spatula. No attempt was made to drain the water, or remove debris, rocks

and small biological specimens. Samples were not collected under areas covered by

moss. Each sample was sealed and immediately stored in an ice chest over dry ice

and thereby quick frozen.

Sediment sampling was done in two

different modes to characterize different

sampling sites. Some areas were characterized by sampling in a small localized

area to help insure uniformity of samples.

Others were sampled by taking a cross- section at regular intervals between the

low- low tide and the line at high tide.

The latter method was used where very- large areas were exposed by changes in

tidal levels. The cross - sectional sam- pling method appears to show a larger

sample variability but was thought to be more representative of the sampling site.

These samples show marked differences in

181
their hydrocarbon profiles because of the

differences in biological content in the

samples, the presence of decaying vegetation, animal wastes, etc., and because

the extent of water coverage varies

markedly, depending upon where the sample

is collected.

No attempt was made in the laboratory to blend all of the samples taken

from a given site because homogenization

of grossly heterogeneous samples is not

feasible. Therefore, each site was characterized by five discrete samples.

Large rocks were not used as part of the

laboratory sample, but otherwise the sam- ple was defined as the sample collected

in the field.

The inner-tidal organisms listed in

Table I were chosed as being representative of the area, because of their differences in feeding and migratory habits,

and reproduction rates, and to coincide

with species for which biological baseline

data was being collected.

Table I. Biological Samples Collected

Biological Form for

Sample Significance Analysis

Macoma

(small clam)

Mytilus

(mussel)

Acmaea

(limpet

Cancer

Magister

(dungeness

crab)

Deposit

Feeder

Suspension

Feeder

Grazing

Feeder

Bottom

Feeder

Frozen, in

shell.

Bissel threads

removed

.

Organism

quantitatively

removed from

shell.

Quantitatively removed

from shell

while frozen.

Tissue, gills

and organs

removed and

homogenized.

Macomas were collected by shoveling

surface sediment into shaker screens

(with 1/4 inch wire mesh) in order to wash out sediment, silt, and small debris

in the tidal water. Large sampling areas

(>^1000 ft ) were needed to collect

quintuplicate samples of 100 g each.

All work was done with pentane rinsed

stainless steel spatulas and polyethylene

gloves. The final sorting of debris and

Macomas was done by hand before quick

freezing the samples over dry ice.

Adult Mytilus and Acmaea were collected directly into the glass jars by

prying them loose with spatulas. Crabs were collected from crab pots and quick

frozen in polyethylene bags. In all cases, 100 grams was required for each

sample of each specimen, and quintuplicates

were collected in all cases. Both sexually mature and immature

Fucus (macro algae) were collected from

different tidal levels at each sampling

site in 64 oz. jars by cutting samples

at the base of the stem. However, it is

very difficult to select a representative

amount of mature Fucus and this error will

be reflected as a sampling bias and give a larger apparent biological variability.

Only Fucus attached to a rock or sediment

base was used in order to avoid drifting

samples and to insure that the sample was taken from a stable colony. It was felt

that a true cross-sectional sample of the

Fucus should be taken to represent changes

in tidal levels and to reflect differences

in exposure to the air, sun, and water.

Finally, an attitude and approach to field sampling has evolved which appears

to be successful. First the design of the

sampling program and the choice of methods

to be used should be implemented in terms

of the methods of analysis to be employed.

Personnel in charge of collecting samples

should be thoroughly familiar with the

precautions to be taken during sample collection and handling, and be cognizant of

the many possible sources of contamination. It has been our experience that

it is highly desirable that the chemists

responsible for the laboratory analysis

participate with biologists in the field

sampling and that good rapport and cooperative working relationships between

field and laboratory personnel be maintained. In this manner, the laboratory

data can be most effectively analyzed in

terms of the limitations and considerations of field sampling. Conversely,

field sampling experiments can be more effectively designed once the errors and

procedures of the laboratory analysis are thoroughly understood.

Key Words: sediment, biological tissue,

baseline studies, sampling, hydrocarbons,

contamination

.

182
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

FIELD SAMPLING METHODS AND TECHNIQUES

FOR MARINE ORGANISMS AND SEDIMENTS

Dale Straughan

Allan Hancock Foundation

University of Southern California

Los Angeles, California 90007

Grice et al ^1_/ reported on the

solution of problems associated with

collection and preservation of open ocean marine organisms for pollutant

analysis. Field sampling programs in inshore and intertidal areas in Southern

California encountered many of the same problems which required similar solutions.

This paper addresses itself to the difficulty in obtaining representative data

to describe levels of petroleum content

of sediments and organisms in an area.

Most of these field sampling problems

are the result of the uneven petroleum

distribution in the marine environment.

This applies to the water column, sediments, organisms and tissues. It is

only in exceptionally large oil spills, near the source of a spill, or in en- closed areas, that large areas are coated

with oil. In the open ocean, soluble

components usually do not reach the ocean

floor except in shallows with high wave

action. However, the circumstance is

different in enclosed areas where the

oil may become trapped or if the oil is

released through cracks in the ocean

floor. As oil which leaks from submarine

faults rises to the surface, some soluble

components enter the water column.

In areas such as Coal Oil Point,

natural petroleum compounds enter the ocean in several different ways:

• gas bubbles which move rapidly to the surface

• oil which moves rapidly to the water surface. (This

could be almost a continuous

flow such as that observed by

divers in June 1973, which

emanated from holes described

as the size of gopher holes

(~7.5 cm. diameter)

• bubbles of oil which gradually appear on the surface

of the substrate and then move to the water surface

• oil which appears on the

sediment surface as a sticky

tar which may gradually float

free to the surface, drift

with negative buoyancy, or simply spread through bottom

sediments.

Location of such emission sites is

frequently difficult because of their

intermittent nature. Hence, a benthic

sampling program could not necessarily

be designed around the detection of active

emission sites at a particular time.

Much of the seep oil and tar from

the Coal Oil Point area may be deposited

in the trough of the Santa Barbara basin

(Fischer and Berry ^2_7) . Kolpack /~3_7

determined that the Santa Barbara basin

contains spill oil , and Oguri ^4_7 re- ported that material in trawls taken in

the Santa Barbara basin was oily.

Therefore, in areas such as the

Santa Barbara Channel, sediments and

organisms will not be evenly exposed to petroleum compounds. This complicates

sampling problems to determine:

1) where to obtain representative

samples of the area,

2) what sample sizes are needed,

3) how many samples are needed,

and

4) when and how frequently samples

should be taken.

A further problem may be created by

periodic exposure to oil. Ampaya and

Mikolaj /_ 5_,/ reported periodic changes

in oil seepage rate based on data from

a seep near Coal Oil Point, whereas the

present author has noted variations in

the amount of tar on sandy beaches adjacent to the Santa Barbara Channel. More

tar was present on beaches towards the

Southern end of the Santa Barbara Channel

in the period March through May than at other times of the year (unpublished data

gathered 1971-74) . This may not be a reflection of wind and current direction.

Areas may also be seasonally or intermittently exposed to oil pollution from

man's activities.

183
A. Location of samples representative

of an area will depend on the size and

geologic setting of the area. For example,

open coastline areas where there are no adjacent sources of oil can doubtless be

characterized by samples at different

depths of both sediments and organisms.

However, sampling of an area of intermittent oil seepage poses a different

problem. The amount of oil in the sediments will vary both horizontally and

vertically. The vertical variation on

a beach will be due in part to a combination of different rates of oil deposition and in part to sedimentary movements.

Table I. Total CCU Extractable

Organics (mg/1 ) in Sediments

Related to Depth in Water

and Sediments.

Water

(m) Sediment

(cm.)

20 40 60

* 0 - 5

5 - 15 565 4,800

4,500

8,100

4,200 8.000

* 0 - 5

5 - 15 285 4.500

22,500

25.000

4,350 6.200

0 - 5 5-15

1.300 4.5005,200 9.2006.600

0 - 5

5 - 15 570 6,100 17.000 60.000

9,800

* Average of duplicate samples.

Table I illustrates the difference

in total CCI4 extractable organic content in box cores of sediments from a natural oil seep area in the Santa Barbara

Channel, as determined by infrared analysis. In all cases, the total organic

content is higher 5-15 cm. deep in the

sediments than in the top 5 cm. of the

sediments. The total organic content is

also lower in the shallow water (20 m.)

samples than in the deeper water (40-60m.)

samples. In all these samples, grain size

is approximately equivalent. These trends

are generally consistent with other available data, but the trend of increasing

total organic content with depth is interrupted by the presence of natural petroleum seeps.

The surface area of a box core was

21 X 29 cms. Duplicate samples were collected in the top 5 cms to determine

the variability over the surface area

(Table II).

Table 11. Total CCla Extractable

Organics (mg/1) in Duplicate

Sediment Samples Collected

in the top 5 cm. of the Box Core Samples.

Sample t Difference

1 110 460 318

2 340 390 15

3 400 730 82

4 3.800 4,600 21

5 4.000 4.700 18

6 4,200 4,800 14

7 5.200 5,800 12

8 20.000 25,000 25

% Difference was calculated on the lowest value.

The variation in this set of 8 duplicate samples collected in an area

of natural oil seepage demonstrates the

danger of using isolated samples as a baseline figure without some idea of_ _

the variability in the area. Juge / 6_/

also reported the variability of petroleum content of sediments within a single

box core

.

Hence an area such as the Santa

Barbara Channel would require;

• a sampling program related

to water depth in non-oil

seep areas to account for

the variation in accumulation

of petroleum with water depth

• a sampling program within one

or more of the oil seep areas

to determine the level of

petroleum accumulation adjacent to oil seepage

• sampling of sediments from

different depths to determine

if there are variations

in petroleum deposition, sand

movement, or surface oxidation

Sediment grain size must be con- sidered in all cases.

B. Sample size should be determined

empirically. The lower limit is determined by the minimal amount of material

necessary for adequate chemical analysis.

Warner / 7_/ determined that, for hydrocarbon analysis of sediments in Southern

California mainland shelf areas, a sample

of approximately 120 ml. is required.

Naturally, less material would be re184
quired for sediments with a high hydrocarbon content than for those with low

hydrocarbon content. However, as the

hydrocarbon content is generally unknown

at the time of collection, this minimal

sample size should be collected.

It is impossible to make a general

rule on optimum sample size. A constant

sample size will result in over-sampling

and an increase in preservation and

storage problems.

Optimal sample size can be determined for each area and/or type of situation. A subjective assessment of sample

size can be determined by analyzing

multiple samples of known volume. The mean is then calculated on a cumulative

basis and plotted against sample volume.

The optimum sample size occurs where

variation ceases and the curve flattens

(Fig. 1) . Naturally, the larger the

sample size, the more accurate the information; but as the curve flattens, the

increase in information decreases and

becomes less important (based on Kershaw

£_ 8_/) . The optimal sample size is

(5x120 ml. = 600 ml.). If these 5 samples

are analyzed separately rather than as a composite, then an indication of the variability in content within a small area will be obtained.

5-

Z

<

<

>

4-

->—I—«—I—I—

r

0 2 4 6

SAMPLE SIZE (X 120 ml)

Figure 1. The reduction of the variations in the value of the mean, as the size of the sample is increased.

C. The number of samples required to characterize an area can be determined

using the same rationale as that used to

determine sample size.

D. Timing and/or frequency of sampling

are less important in the open ocean, where seasonal effects and man's activities are least variable. However, changes

in ocean currents could result in seasonal changes in exposure of sediments

and organisms to petroleum hydrocarbons.

In nearshore areas, where seasonal trends

are greater and where pollution will have

a greater effect on the environment,

sampling should be seasonal.

Sampling of tissues

The same procedure should be used

to determine the distribution, size,

number, and frequency (timing) of sampling

animals. The minimal sample size of

tissues used in the field sampling program

in Southern California was 10 gm. While

this was more than adequate for tissues

containing high levels of petroleum hydrocarbons, it was only adequate to hydrocarbon levels as low as 2 ppm.

Containers and Preservation Methods

All sediment and tissue samples were frozen. Samples were retained in

a normal freezer (-20°C) or on dry ice

during field trips and transportation,

but long term storage was in a freezer

maintained between -70° and -80°C. This

low temperature was used to eliminate

changes due to biological processes which

can occur at "hous^ehold" freezer storage

temperatures ^9_/.

This method of preservation imposed

some limitations on the type of storage

containers used. For example, some glassware could not withstand these low temperatures. Other sampling containers found

to be unsuitable included aluminum foil

and paper — the former because foil is

often coated with oils or grease during

manufacture and the latter because it

tends to stick to tissues during freezing

and thus contaminates the samples. Plastics other than Teflon were generally

not suitable for storage or collection.

Clean aluminum cans and glassware were used for sediments and tissues re- spectively. Cans and glassware can be

adequately cleaned prior to use.

185
Contamination of samples results from:

1. contaminated collection equipment,

2, preparation of samples for preservation,

3, passage of sampling equipment

through surface slicks,

4. boat exhausts.

These problems were detailed by Grice

et al. /~1_y.

In intertidal areas, hand tools can be cleaned between collection of samples.

Visible compounds can be scrubbed from

the surface of such equipment using

detergents, and then rinsed well in

clean water and acetone and finally

dried.

Sampling to determine the presence

of petroleum in animal tissues involves

several unique problems. Foremost is

the difficulty in insuring that the

petroleum is in the tissues rather than

passing through the gut at the time of

collection. If the animal is large, it can be dissected and the gut contents re- moved. However, sampling benthic infauna provides a further challenge. The

animals are generally very small and many

of them feed by passing sediments through

their gut. In a heavily contaminated

area, only a few grains of sediment

either on the animal or in the gut in- creases the error of hydrocarbon tissue

analysis to an unacceptable level.

Assuming that all external sediments

are removed, the problem of removing

sediments from the gut is of paramount

importance. Dissection of fresh animals

of this size (possibly only a few mm. wide and/or long) is impossible on a ship and dissection after freezing is

impossible because the freezing process

damages tissues. Dissection also results

in loss of body fluids. This is unacceptable in small animals with a high percent

of body fluids.

A more practical method is maintance

of small live organisms in clean seawater

to allow them to eject gut contents prior

to preservation. If this is done in a closed container, the animals may re- ingest their faeces. Hence, such a program should involve a running seawater

3ystem with some method of removing defecated material. This is not as simple

as it appears, because egested material

is frequently almost as large in diameter

as the body of the animal (polychaete)

from which it originated.

Just how significant contamination

could be can be demonstrated by data

from trial analyses of sediments con- taining 4,100 mg/g total CCl^ extractable

organics. A value for extractable or- ganics as high as 1,000 >ag/g was recorded

in the detritus removed externally from

the animals in one sample, while only

40)ig/g extractable organics was recorded

in the animals.

It is apparent that only a very small

amount of sediment in the gut of these

animals can render the value meaningless.

While the actual percentage of contamination in the tissues is unknown, it is

obvious that this particular infaunal

sample had a very low level of contamination compared with the surrounding

sediments.

Use of a continuous flow-through

system such as used in depuration experiments, is suitable for larger animals

such as mussels. However, such a system

needs careful experimentation to determine the time required to remove only gut

contents without depuration of petroleum

compounds from the tissues. Depuration

of some petroleum compounds can occur within a matter of hours (Anderson ^10_7').

An additional problem involves con- taminated water trapped' within molluscan

shells. Here the proble^o is not as critical as in the case of sedi-ments, because

the concentration of petroi^.eum in seawater

is probably lower than that found in

organisms. However, this water should be

carefully removed prior to t.issue analyses. After freezing, this cai-, easily be

accomplished by simply removin-iJ all the

ice when the shell is opened foe tissue

analysis

.

Acknowledgments

Data and observations reportedjjin

this paper were made possible throuch

financial support from the NOAA Offi^^e

of Sea Grant, Department of Commerce

under Grant #2-35227 to the Universiti^

of Southern California, Western Oil anc Gas Association, The American Petroleum

Institute and the Southern California

Edison Company.

186
References:

1_/ Grice, G. D, , Harvey, G. R. , Bowen,

V. T., Backus, R, H. , The Collection and Preservation of Open

Marine Organisms for Pollutant

Analysis, Bull. Environ. Contam . Toxicol . , 2' 125-132 (1972).

/_ 2_/ Fischer, P. J. and Berry, R.

,

Environmental Hazards of the Santa

Barbara Channel: Oil and Gas Seeps

and Holocene Faulting, in Geology, Seismicity, and Environmental Im- pact , Moran, D. E., Slosson, J. E.,

Stone, R. O., and Yelveston, C. A.,

Eds. pp. 417-431, AEG Spec. Pub.

University Publishers, Los Angeles,

California (1973).

/_ 3__/ Kolpack, R. L. , Ed., Biological

and Oceanographical Survey of

the Santa Barbara Channel Oil Spill

1969-1970 , Sea Grant Publication

No. 2, Allan Hancock Foundation,

University of Southern California,

Los Angeles, 90007 (1971).

/_ 4_/ Oguri M. , personal communication

(1969)

.

/ 5_y Ampaya, J. P. and Mikolaj, P. G.

,

Tidal Effects on the Activity of

Natural Submarine Oil Seeps: Preliminary Results. Marine Tech .

_ Soc. J . 7, (1), 25-28 (1973).

/_ 6_/ Sister Damien Marie Juge, A Study

of the Bacterial Population of

Bottom Sediments in the Santa

Barbara Channel after the Oil

Spill, in Biological and Oceanographical Survey of the Santa

Barbara Channel Oil Spill 1969-

1970 , Straughan, D. , Ed. Vol. 1,

pp. 179-222, Sea Grant Publication

No. 2, Pub. Allan Hancock Foundation, University of Southern California, Los Angeles, California

90007 (1971).

/ 7_/ Warner, J. S. personal communication (1972).

/_ S_/ Kershaw, K. A., Quantitative and

Dynamic Ecology , Edward Arnold

(Publishers) Ltd., London. (1964).

/_ 9_/ Jefferies, D. J., Walker, C. H.

,

Uptake of pp-'--DDT and its PostMortem Breakdown in the Avian Liver,

Nature , 212 , 533-534 (1966).

/lO_/ Anderson, J., Accumulation and

Discharge of Petroleum Hydrocarbons

by Shellfish , presented at Department of Interior Public Hearing

on the Development of the Santa

Ynez Unit conducted at Santa

Barbara, California, October 1, 2,

1973. (1973).

187
jI N
HBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

METHODS FOR ESTABLISHING LEVELS OF PETROLEUM

CONTAMINATION IN 0R(;ANISMS AND SEDIMENT AS RELATED

TO MARINE POLLUTION MONITORING

R. C. Clark, Jr.

National Marine Fisheries Service

Northwest Fisheries Center

2725 Montlake Boulevard East

Seattle, WA 98112 U.S.A.

Petroleum hydrocarbons in marine organisms and sediments have been extracted, separated, iso- lated, identified, and quantified by a number of methods. Since no single technique provides a complete analysis of petroleum residues in organisms, some consideration for selecting methods

and for understanding potential problem areas are presented.

Petroleum is derived from the decomposition,

at high temperatures and pressures, of plants and animals buried for millions of years. Hydrocarbons are not foreign to the marine environment; they are synthesized by most, if not all, living

organisms. Several detailed reviews of the distinqulshlng characteristics between hydrocarbons

native to marine organisms and sediment and those found In petroleum have been prepared [l], [2],

[3].

In order to decide what combination of ana- lytical procedures will be most useful, the analyst needs to determine the level of sensitivity and selectivity necessary to meet the requirements of his scientific goal. For example,

If one wishes to demonstrate only high-level

uptake (> 10"^ g/ g wet weight, yet below detectable odor and taste levels) of certain petroleum

components in marine tissue, then less sensitive

techniques need be used than if lower biogenic

levels (10"^ g/g wet weight or less) are investigated.

Contamination

Fossil hydrocarbons are ubiquitous compounds

which can cause serious problems and create artifacts for the unwary in the laboratory. Once the analyst has established his lower limit of sensitivity (or detectabllity) , then contamination of solvents and chemicals must be investigated. True biogenic baseline levels of hydrocarbons are only

obtainable by purifying solvents and chemicals.

Table I lists some typical levels of n-paraffin

hydrocarbon contamination routinely found in laboratory chemicals, solvents, and materials.

To Insure that contaminants do not exceed levels which would make the isolation of the same com- pounds from organisms meaningless, it Is essential that the complete extraction and analytical proce- dure be carried out routinely without the sample. A rule of thumb might be that the solvent/chemical

blank should contribute less than 10% of the total signal from an organism sample.

Extraction

Before the sample is extracted, the actual method of weight determination must be expressed

on some standard weight/weight basis. If wet weight is chosen as a basis, then the moisture

content of the sample should be provided. If the sample has been frozen, body fluids contained in the frozen aqueous portion from ice-ruptured

membrane and cellular structures should not be lost during a draining step.

A number of methods have been presented

(table II, based on the background material

presented in references [2] and for removing

the lipid fraction from biological and sediment

samples containing hydrocarbons. Soxhlet extraction of minced, homogenized, or sonified tissue

samples is routinely used for removing lipids

with a recycling solvent system. Schmid, et al. [5] experimentally applied solubility parameter

theory to the properties of solvent extraction

from moist biological membranes and found that

the successful separation of lipids from proteins

in undenatured membranes required (1) solvation

of the water in the organic phase of the extracting solvent system, and (2) optimal solubility

for both the relatively nonpolar neutral lipids

and for polar lipids. Their studies indicated

that a binary solvent system using an aromatic

hydrocarbon and a low molecular weight alcohol proved efficient.

Table I. Typical levels of background

hydrocarbcn contamination in laboratory

chemicals, solvents, and materials (extracted with

benzene, expressed as ri-C^^-C^-^). After

Chemicals/ Solvents Found Purification

Glass-distilled, commercial Pentane Benzene

Cold tap water (in pentane)

Brand A

Brand B Brand C Brand D MgSO^ , anhydrous

Sand, Ottawa

NAOH, dissol.

12,

10, tap water

56.2 IJ-g/1 <2.5 IJ.g/1 100 Hg/1 <2.5 M.g/1 0.92 IAg/l 30-35 ng/g 12-18 ng/g

17 ng/g

108 ng/g

245 ng/g

1-130 ng/g 4.8 ng/g

1-369 ng/g 4.9 ng/g

<5 ng/g

Materials

Aluminum foil Brand A

Brand B Asbestos cord

Glass fibre (wool) 1st extr

2nd extr Glass microbeads 1st extr

2nd extr Laboratory wiping tissue

Rinsings from fingers

Rinsings from rubber gloves

Soxhlet thimble, Nichrome wire

Cereunic, 1st extr. 2nd extr. Teflon(R)3rd extr. 4th extr. 5th extr.

7.1 ng/cm2

8.6 ng/cm

^5 ng/g

18.3 ng/g

1.96 ng/g

50.9 ng/g

6.69 ng/g

2 197 ng/cm

100 M^g/ finger

230 lig/ finger

1,589 ng/ thimble

1,309 ng/ thimble

444 ng/ thimble

346,400 ng/ thimble

40,660 ng/ thimble

2,042 ng/ thimble

189
Table II, Extraction teehniquea of petroleum components from biological and sediment materials.

Extraction Sample Equipment

Technique

1. Soxhlet apparatus with

MeOH, benzene, combination or other solvents

of similar polarity.

2. Bonification , solvent

extraction with CCl^

and solvent above.

3. Steam distillation

coupled with solvent

extraction, ethyl ether.

A. Hprnogenatlon, anhydrous

NajSO^ to promote cell disruption and remove

water; solvent extraction:

pentane or hexane.

5. Homogenation , anhydrous

MgSO^ and sand; hexane.

6. Digestion In alcoholic K)R

7. Solvent extraction

followed by saponlficatlofi.

8. Helium stripping at 120°; water and hydrocarbon

traps, gas chromatography.

9. Nitrogen stripping at 20°,

stirred aqueous solution;

GLC/MS.

10

Application

Frozen samples

Lyophllized samples Wet or fresh samples

Requirements

As little as 1 g. wet or fresh; rou- tinely 10-40 g. wet

Frozen samples Wet or fresh samples

Frozen samples

Lyophllized samples Wet or fresh samples

1-10 g. wet or fresh weight

As little as 1 g. wet or fresh; rou- tinely 10-40 g. wet

Lipid extract

Sediments, wet

Sediments, wet

Sediment, dry

10"^ g.

0.5 g. Detect 1 ppm

0.05 g. Detect 1 ppm

Heat sample and vaporize

directly into Inlet system of MS> Source: Based on background material presented In references [2], [4].

Requirements

Soxhlet apparatus;

separatory funnels; rotary evaporator

for concentrating

extract. Sonicator probe or sonicator bath; separatory funnels,

rotary evaporator.

Extraction flasks; steam distillation

apparatus.

Blender or homogenizer;

tissue grinders or similar equipment.

Mortar and pestle.

Apparatus for refluxlng. Screw can centrifuge

tube with Teflon®

liner; centrifuge.

Gas systems, efficient

trapping materials;

gas chromatograph.

Same as above; mass

sp ec trome try

•

Mass spectrometry.

For certain fat-rich samples, Soxhlet extrac- tion may not be as efficient or as rapid as an alkaline digestion. An alkaline digestion, or saponification of a previously concentrated lipid

extract, also permits the removal of fatty acid esters which may Interfere with subsequent chro- matographic separations. On the other hand, if an analyst needs to extract a wide range of samples (fresh, frozen, soft- and hard-bodied

organisms, algae, sediments and aged petroleum

residues) by a single procedure, then a Soxhlet

extraction provides a suitable method for almost

all types of environmental samples. Homogenlzation of wet, soft tissue in the presence of Na2S04 or MgS04 Is a rapid method, but extraction

efficiency with the commonly-used nonpolar sol- vents may not be as great as with mixed solvent

systems.

Lov7 molecular weight hydrocarbons from sedi- ments can be obtained semlquantatlvely with gas stripping combined with collection in micro gas chromatography columns or cold traps. This

trapped material can then be flashed Into a gas chromatograph or into a mass spectrometer; the entire sample is consumed in a single analytical

determination. It is Important to remove ele- mental sulfur from sediment extracts prior to hydrocarbon analysis to avoid Interference.

Chromatography

The characteristics of the separation of the lipids into hydrocarbon classes depend upon the choice of chromatographic techniques (table III).

Thin-layer chromatography (TLC) and paper chrom- atography provide simple and rapid separations of hydrocarbon classes from non-hydrocarbons, and a TLC plate can be used with ultraviolet or fluor- escence spectrophotometry or with H2SO4 charring

to produce quantitative estimate of specific

hydrocarbon classes or groups of compounds.

However, for biogenic baseline levels these methods usually lack the precision, specif ity,

sensitivity, and accommodation to sample size

loading available with column chromatography.

High pressure liquid and gel permeation chrom- atography are useful techniques which may gain

wider acceptance in the future.

If one decides to use liquid-solid (column)

chromatography, it is necessary to choose the proper adsorbent or combination of adsorbents with the most advantageous activity and mesh size for the length and diameter of the column. Additional decisions must be made as to loading

(adsorbent/sample: v/w), solvent systems and fraction volumes. Column chromatography commonly

uses silica gel for separating hydrocarbons from

190
Table III. Chromatographic separations of petroleum components from biological and sediment

materials.

Separation

Technique

Column chromatography

Thin-layer

chromatography

3. Paper chromatography

4. High-pressure

liquid chromatography

Components

Separated

Hydrocarbon- type analysis

to alkanes, alkenes,

aromatics, and from

N, S, 0 heterocyclics

Hydrocarbon" type analysis

Ring number separation of

aromatics; separation by

hydrocarbon types

Application

Biological

and sediment

material

extracts

5. Gel permeation Molecular weight Primarily for chromatography separation heavier molecular weight

components

Source: Based on background material presented in references Cz], [4].

Sample

Requirement

10'^ g.

10"^ g.

lO^'^-lO*^

lO'^^-lO"^

Equipment

Requirements

Standard column

chromatography

Standard TLC chromatography

equipment; UV

and densitometer

Standard paper

chromatography

equipment

High-pressure

liquid

chromatograph

GPC equipment

non-hydrocarbons or alumina for separating high

molecular weight polar compounds; a dual column

of altamina packed above silica gel successfully

takes advantage of both adsorbents. Deactivation

of the adsorbents with water (to 5%) prevents

formation of hydrocarbon artifacts from biogenic

hydrocarbons. Nonpolar solvents (usually pentane

or hexane depending on degree of volatility

desired) can be used to elute the saturated hydrocarbons from the column, and the application of more polar solvents (benzene, CCI4, CH3OH, acetone) allows the removal of the more polar hydrocarbon

and non-hydrocarbon compounds. The efficiency of the packed column must be determined occasionally

with standard compounds.

Identification and Quantification

Again, a variety of techniques have been

tried (table IV) for identifying and quantifying

petroleum residues in biological samples and sediments. Gravimetric methods for quantitatively

determining petroleum pollution are useful only

with relatively high concentrations (10"^ g) of a total fraction weight. Spectrophotometric methods usually provide rapid estimates of the total ab- sorbance or fluorescence of all materials at a specific wavelength, but they give little indication of the complexity or molecular "weight range

of a sample. These approaches provide limited

discrimination between biogenic hydrocarbons and those contributed from petroleum pollution. If a known pollutant with a reproducible absorbance or fluorescence characteristic is present (from an

oil spill or bioassay experiment), then spectrophotometric methods are often used as quick,

simple and sensitive monitoring tools.

Gas chromatography provides both a separation

and a quantitative estimate of specific compounds

based on their boiling points and polarity with

TOOOi

- r^- 1 1 1 1 r- 12 16 20 24 26 32 36 CARBON ATOMS / MOLECULE

Figure 1. Typical gas chromatograph calibration

curve using parameters given in table V, based

on nine (9) determinations over a 7-day period.

Symbols represent the range, mean and standard

deviation; average percent std. dev. (1007. x

std. dev. /mean at each carbon number) was 11.47.; curve fit by eye. Individual hydrocarbon con- centrations were 1.015-1.396 (ig/ injection.

191
Table IV. Quantitative techniques for the identification

and sediment materials.

Identification

Technique

1 . Gravimetric

2. UV absorption

spectrophotometry

3. Infrared spectrophotometry

4. Fluorescence

spec tropho tome try

5. Gas chromatography Low resolution

High resolution

6. Mass spectrometry

Gas chromatography/

mass spectrometry

Components

Determined

Non-volatile extractables

Conjungated polyolefins;

aromatic

s

C-H and C=0; C-H stretchfreq. (2,930 cm-1) Total hydrocarbon

Unsaturated compounds;

aromatic

s

Individual hydrocarbons

Hydrocarbon profiles and boiling range of sample More detailed hydrocarbon

profiles; sulfur profiles;

n-paraff in/ Isoprenoid

ratios; depends on column

and on detector. Hydrocarbon types and molecular Identification

of petroleum components in biological Extract

Equipment

Required

Sample

Size 10"^-10"^

10

10-

10

10

10"^ g.

-9 10

10-^ g.

10-^ g.

g< Glassware, analytical balance Micro balance

UV absorption spectrophotometer; Low resolution infrared

spectrophotometer

High resolution IR spectrophotometer with

scale expansion

Fluorescence spectrophotometer

Gas chromatograph

Source:

Preselected hydrocarbons

boiling range C^_3q

Based on background material presented in references [2], [4].

Low resolution MS of 60-600 mass range

GC/MS Interface with

digitizer and/ or computer

respect to the column liquid phase and to the type and resolution capability (packed, capillary,

surface-support coated, etc.). The gas chromatograph can provide, in its simplest form, a "fingerprint" of the components in the sample; more detailed data, requiring additional expenditure of time, can provide substantial information

on individual hydrocarbons which can indicate the origin of the materials. Any detailed study into petroleum uptake in marine organisms and in sedi- ments should consider the incorporation of mass

spectrometric identifications, especially in the use of computerized gas chromatograph/ mass spec- trometer systems. However, this tool should be used to complement existing methods which allow

for more rapid and less expensive analyses of large numbers of samples.

The chemical composition and molecular weight

range of the hydrocarbon fraction reported by

whatever method used must be specific, such as n-paraffins, saturates, olefinlcs, aromatics,

fluorescence materials, etc. It is also necessary to state the precision, accuracy, and the lower limit of sensitivity of the method used; one example of the latter using gas chromatography is given in table V under typical biogenic baseline operating conditions for ii-paraffin

hydrocarbons. Calibration of ri-parafflns by

routine gas chromatography can give a curve (fig.1) showing decreasing sensitivity with increasing carbon number so that calibrating a chromatogram

at a single carbon number may lead to quantitative errors. Reproducibility and recovery of

Table V. Typical lower detection limits

by gas chromatography b/ .

Carbon number Routine — Maximum

13 8 4

14 8 4

15 4 2 16 4 1 18 2 1 20 2 1 22 2 1 24 2 1 28 2 1 32 8 3 36 16 8

a/ Experimental conditions: Varian Aerograph

model 1200; linear-programed temperature 6 / mln. , 60-332 C; hydrogen flame ionization

detector; Injector 300°C; detector 360°C; N2 29 ml/mln, H2 28 ml/ mln; air 240 ml/mln;

1.9 m. X 0.32 cm CD stainless steel column,

1.57. RTV 502 silicone rubber on Chromosorb

G H.P. , 80/100 mesh; 1 mv recorder 0.63 cm/ mln; automatic attenuator; instrument atten- uator 8x on range 1 (8 x 10"^2 amps).

hj In nanograms , based on minimum peak area of

6 square units (1 unit = 0.02 inches).

hydrocarbons added to biological samples should

also be established. An example is given in an accompanying paper

192
10,000

5,000-

2,000-

1.000

500

200

100

50-

20-

10-

5-

2

-'

0 North Point - F«b 1972

1 North Point - Moy 1972 Mukkow Boy - May 1972

o North Polnl-MukkowSoy (May 1972)

• Fr««h Tar Boll S E Wrtck Cove

—I I I I

1 I I I I I 10 14 18 22 26 30 34 CARBON ATOMS / MOLECULE

38 14 18 22 26 30 34 CARBON ATOMS / MOLECULE

38

Figure 2. Paraffin hydrocarbon patterns for goose barnacles ( Mitella polymerue ) exposed to Navy Special

Fuel Oil from the GENERAL M. C. MEIGS. A: Exposed samples compared with a control sample.

B: The "residual" hydrocarbon pattern obtained by subtracting the control sample hydrocarbon

values from the exposed is compared with the Navy Special Fuel Oil residue pattern LSJ.

Data Reduction

In an environmental monitoring program, It is ultimately necessary to indicate whether petroleum

pollution has occurred and to what extent it has been incorporated into biological populations and

sediments. An example of some of the numerical

calculations that have been tried on paraffin

hydrocarbons is given In an accompanying papert9].

Other parameters which can be used on homologous

series include the Odd-Even Predominance [lOj and the calculation of "residual" hydrocarbon patterns

(fig. 2 and [8], [ll]).

Limitations

The absence of certain petroleum hydrocarbon

classes in marine organisms does not necessarily

prove the absence of petroleum pollution. In cases where the petroleum pollutant is low In paraffin hydrocarbons, paraffin hydrocarbon patterns may not be useful C?]. Aromatic hydrocarbons, which are a biogenic rarity yet often a major component in petrolevmi and its refined

products, may be rapidly lost from contaminated

organisms [l2], [l3J, [l4], [l5] so their utility

in marine pollution monitoring programs may be

somewhat limited. These facts point out the need

for research into the uptake, retention, and discharge of petroleum components by marine organisms before undertaking large-scale monitoring

programs.

In order to plan a global pollution monitoring program for petroleum, we need to standardize

sample collection, preservation and preparation,

including a consistent scheme of sample weighing

for marine organisms and sediments. We need to standardize extractive and chromatographic procedures and data reduction techniques so that the resulting data are compatible worldwide.

References:

[l] Farrington, J. W. , Giam, C. S., Harvey, G. R., Parker, P. L. , and Teal, J., Analytical

techniques for selected organic compounds,

in Marine Pollution Monitoring: Strategies

for a National Program, Goldberg, E. D. , Ed.,

Workshop at Santa Catallna Marine Biological

Laboratory 25-28 Oct., pp. 152-176 (1972).

[2] National Academy of Sciences, Petroleum in the Marine Environment, Report from the Workshop on Inputs, Fates and Effects of

193
Petroleum in the Marine Environment, Ocean Affairs Board, Washington, D. C. (in press),

(1974).

[3] Marine Technology Society, Report from the Marine Bioassay Workshop, 9-11 April,

Montauk, N. Y. , (in preparation), (1974).

[4] Background papers and reports of the Chemical

Techniques Group for reference [2] above: Weiss, F. T. , Farrington, J. W. , Levy, E. M.

,

Adlard, E. R. , and Brown, R. A. (1973).

[5] Schmid, P., Calvert, J., and Steiner, R.

,

Physiol . Chem. & Physics 5, 157-166 (1973).

[5] DiSalvo, L. H. , Guard, H. E. , Hunter, L.

,

and Cobet, A. B. , Hydrocarbons of suspected

pollutant origin in aquatic organisms of San Francisco Bay: Methods and preliminary

results, in The Microbial Degradation of Oil

Pollutants, report from a workshop at Georgia State Univ., 4-6 Dec, Aheam, D. G. , and Meyers, S. P., Ed., pp. 205-220 (1973).

[7] Clark, R. C. , Jr. and Finley, J. S. , Techniques for analysis of paraffin hydrocarbons and for interpretation of data to assess oil spill effects in aquatic organisms, in Proceedings of the 1973 Joint

Conference on Prevention and Control of Oil Spills, pp. 161-172, American Petroleum

Institute, Washington, D. C. (1973).

[S] Clark, R. C. , Jr., Finley, J. S.

,

Patten, B. G. , Stefani, D. F., and

DeNike, E. E. , Interagency investigations of

a persistent oil spill on the Washington

coast, ibid, pp. 793-808 (1973).

[9] Clark, R. C. , Jr. and Finley, J. S.

,

Analytical techniques for isolating and quantifying petroleum paraffin hydrocarbons

in marine organisms, this proceedings.

Q.O] Scalan, R. S. and Smith, J. E. , Geochtm. Cosmochim. Acta 34 , 611-620 (197071

[11] Clark, R. C. , Jr. and Finley, J. S.

,

Mar. Poll . Bull . 4, 172-176 (1973).

[12] Lee, R. F. , Sauerheber, R. , and Dobbs, G. H. Marine Biology H, 201-208 (1972).

[13] Stegeman, J. J. and Teal, J. M. , Marine

Biology 22, 37-44 (1973).

[14] Anderson, J. W. , Uptake and depuration of specific hydrocarbons from oil by the bivalves Rangi a cureata and Crassostrea virginica , in Collected Background Papers,

pp. 690-708, reference [2] above (1973).

h.5] Roubal, W. T. , (Unpublished), NMFS (1974).

Key Words: Analytical techniques, chromatography,

hydrocarbons, marine organisms, oil pollution,

paraffin residual patterns, petroleum contamination, sediments.

194
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

QUANTITATIVE DETERMINATION OF

HYDROCARBONS IN MARINE ORGANISMS

J. S. Warner

Battelle Columbus Laboratories

505 King Avenue

Columbus, OH 43201 U.S.A.

Assessment of the extent and effects of contamination of the marine environment by

petroleum fractions or crude oils requires a knowledge of the petroleum hydrocarbon uptake

by marine organisms. Because of factors such

as seasonal variations, discontinuous feeding

habits, differences in life stages, specimen

variability, and varying environmental stresses, numerous samples need to be analyzed in order

to obtain reliable and meaningful results. The

purpose of this paper is to describe reliable

analytical methodology that is diagnostic for

individual hydrocarbon components and applicable to the analysis of relatively large numbers

of samples.

The procedure involves aqueous caustic

digestion, ether extraction, silica-gel chromatography, and gas chormatography. Ten grams

of homogenized tissue is mixed with four grams

of 4N NaOH in a 50-ml screw-cap centrifuge tube

and heated at 90 C for two hours. The digest is extracted with 25 ml of peroxide-free ethyl ether

in two portions. The combined extract is concentrated to one ml, the ether is replaced by

hexane, and the resulting hexane solution is cleaned up and fractionated by column chromatography using 0.9 x 2 5 cm column containing

10 g of silica gel activated at 150 C. Three

fractions are collected. Fraction 1 is eluted with 25 ml of petroleum ether; fractions 2 and 3 are each eluted with 25 ml of 20 percent methylene chloride in petroelum ether. After adding

100 /ig of n-dotriacontane as an internal standard

each fraction is concentrated to 200 jil and a

2 jUl aliquot is used for gas chromatographic

analysis.

The method of concentration was found to be extremely critical if losses of naphthalene

and similarly volatile components is to be avoided. The sample is contained in a 25 -ml

evaporator tube fitted with a modified Snyder

column and concentrated by heating with a Kontes

tube heater that is modified to permit heating

from the bottom tip of the tube.

For the gas chromatography a 3. 5 m x

2 mm I. D. glass column packed with 3 percent

OV-1 or 3 percent OV-17 on 100-120 mesh Gas

Chrom Q is used with the column temperature

programmed from 60 to 300 C at 8 degrees per

minute. Fraction 1 contains all of the saturated

hydrocarbons; fraction 2 contains most of the mono- and diaromatic hydrocarbons as well as most of the biogenic olefins; and fraction 3 contains

most of the tri- and polyaromatic hydrocarbons and

and small amounts of biogenic olefins.

The recovery of hydrocarbons by this procedure was checked by analyzing oyster tissue to which known amounts of 1 , 2, 3, 5-tetramethylbenzene, 2-methylnaphthalene, 2, 3, 6-trimethylnaphthalene, fluorene, phenanthrene, and n- tetracosane had been added. As shown by the data

in table I which gives the averages of three determinations, recoveries were greater than 90 percent

except at the 0.2 j^g/g level.

Table I. Recovery of Hydrocarbons from Spiked

Oyster Tissue

AVERAGE % RECOVERY AT GIVEN LEVEL COMPOUND 10 ng/g 1 Mg/g 0.2 /ig/g

1,2,3,5,-82 97 ± 2 91+5 68 ± 6 2-MN 99 ±2 96 ±4 74 ± 13

2,3,6-TMN 99 ± 1 99 ±2 92 + 3

Fluorene 95 + 1 99 ±2 95+3

Phenanthrene 99+2 94 ± 2 106 ±5

C24 95 ±2 97 ± 1 100+3

a = Biphenyl = 0 22 /xg/g

b = Methylbiphenyl = 0.25/ig/g

c = Fluorene = 0.46 /ig/g

d = Methylfluorene = 0.54 ^g/g

e = Phenanthrene = 0,88 /xg/g

f = Methylphenonthrene = 0,56 /^g/g

g = Cg- Phenanthrene = 0, 1 3 /ig/g

10 15 20

Retention Time, minutes 25

Figure 1. Gas Chromatogram of Fraction 3 from

Clams Exposed to a Fuel Oil

195
Figure 2. GC-MS of Fraction 3 from Clams Exposed to a Fuel Oil

Figure I is a representative gas chromatogram of a tissue extract containing low levels of hydrocarbons. This is a fraction 3 obtained from

clams that had been exposed to a fuel oil.

The individual aromatic hydrocarbons were

tentatively identified by using gas chromatography combined with chemical ionization mass

spectrometry. The reconstructed gas chromatogram obtained by GC-MS of fraction 3 obtained

from clams exposed to a relatively high level of a fuel oil is shown in figure 2. Biphenyl,

fluorene, dibenzothiophene, and phenanthrene,

and their methyl- and dimethyl- derivatives are

indicated by the appropriate abbreviations.

We have used the overall extraction — gas chromatographic procedure on several hundred

tissue samples including mussels, lobsters,

clams, oysters, fish, shrimp, abalone, crabs,

starfish, sea urchins, and bloodworms. Except

for certain abalone viscera samples which contained high levels of interfering carotenoids, the method has been very satisfactory.

This work was supported by the American

Petroleum Institute under Contract No. OS-20-G.

Tissue samples were submitted by Prof. Jack

Anderson of Texas A&M University under API

Contract No. OS-20-C and Prof. Dale Straughan

of the University of Southern California under

API Contract No. OS-20-D.

Key Words: Aromatic hydrocarbons, gas chromatography, marine organisms, mass spectrometry,

silica gel fractionation, tissue extraction.

196
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

METHODS FOR TRACE ORGANIC ANALYSIS

IN SEDIMENTS AND MARINE ORGANISMS

H.S. Hertz, S.N. Chesler, W.E. May,

B.H. Gump, D.P. Enagonio,

and S.P. Cram

Analytical Chemistry Division

National Bureau of Standards

Washington, D.C. 20234

The Prudhoe Bay area of Alaska is

estimated to contain at least 10 billion

barrels of crude oil. This crude oil is to be transported via pipeline to the

ice-free port of Valdez on Prince William

Sound, from which point it will be shipped via tanker to refineries and distribution facilities in the United States.

Tanker traffic, oil transfer, and

ballast treatment facilities in Port

Valdez are likely to increase current

levels of hydrocarbons in the environment

For this reason, a chemical baseline

study (prior to the completion of the

Alaskan Pipeline) of the aromatic hydrocarbon levels in sediment and marine or- ganisms in the Prince William Sound area

is in progress. It is the aim of this

project to determine aromatic hydrocarbons at the part per billion (ppb) level.

Aromatic hydrocarbons were chosen as petroleum indicators, due both to their

supposed toxicity and to their insignificant biogenic levels.

A technique for the isolation and

measurement of trace organics present

on sediment has been developed and a similar technique for trace hydrocarbons

in marine organisms is currently being

developed. These techniques are the

subject of this paper.

Experimental - The techniques and

necessary precautions for the collection

of samples (sediment, Fucus algae, mussels, and Macoma clams) from eight sites

in the Prince William Sound are described

by Bruce [1] in another paper presented

at this meeting. Immediately after

collection, the samples are quick frozen

and transported in dry ice to the National Bureau of Standards, where they are stored at -50°C.

As part of the sample preparation

procedure all glassware is first cleaned

with soap and water and then placed in a hot concentrated sulfuric acid bath

(100°C) for a period of at least 30 minutes. The glassware is then rinsed sev- eral times with house-distilled water

and finally rinsed with specially prepared in-house water. This in-house

water is also used in the sample analysis and is prepared by redistilling

house-distilled water over KMnO^/KOH.

The distillate is then passed through a 90 X 2.5 cm column packed with XAD-2 [2]

resin for final removal of any remaining

traces of organic compounds. The water

is then redistilled to remove particulates picked up from the XAD-2 resin.

Reagents for the analysis of sediments

include methanol, methylene chloride and

n-pentane, and are singly or doubly

distilled before use. When used, Soxhlet

thimbles are pre-extracted with methanol

§ nethylene chloride, to remove any or- ganic contaminants which would subsequently interfere in the analysis.

TENAX [3] pre-columns are flash-heated

at SSCC for 20 minutes in order to drive off adsorbed organics.

The analysis scheme for sediments is

outlined in figure 1. The method involves the headspace sampling by a stream

of purified nitrogen and trapping on a TENAX pre-column in preparation for gas

chromatography. The residual sample is

then Soxhlet extracted with methanol

followed by methylene chloride. The

details of the analysis are described

below. Normally, either six samples or five samples and a blank are run simultaneously.

Samples are thawed and transferred

to the separation flask in a class 100

laminar flow, clean air hood located in

SAMPLE PREPARATION

SEDIMENT SAMPLE

Vaport

Clean air at 4°C

Closed system

T = 4 — /O'C

» = 3 hrs. liq.

TENAX

I GC

Aq.

Filter Solids

Discard

CH^Ij

Extract

Org.

MeOH

Soxhlet

CH^Ij

S"*''''' Solids

Vacuum Distill n - Cj Extract 1

Sample

Dry Weight GC

Figure 1. Analytical scheme for the

preparation and analysis of sediment samples.

197
a cold room maintained at 4°C. Pure

water (600 ml) and an internal standard

containing several aromatic hydrocarbons

(each at a concentration of 10 ppb) are added. The flask is then stoppered and

transferred to an organic "clean lab" for

sample extraction.

The flask is placed in a heating

mantle mounted on a magnetic stirrer.

One port of the flask is connected to the prepurified nitrogen line which

directs a stream of gas across the liquid

interface at a flow rate of '\'180 ml/min.

A second port contains the exit line,

which is connected to a 6 x 0 . 6 cm stainless steel Swagelock- fitted column packed

with TENAX used for trapping the outgassed organics. This column is mounted in

a cylindrical jacket which is chilled by

a steady stream of cold air. Samples are outgassed for three hours, first at room temperature, and then while gradually

raising the temperature to 70°C.

At the end of this period the nitrogen gas is diverted from the flask directly to the TENAX column for 2 hours in

order to dry the column. The dried col- umn is capped and taken to the instrument

lab for analysis.

The residual sediment and water are then poured through a clean, dry, weighed

Soxhlet thimble and the contents of the

thimble extracted with methanol for 4 hrs. This step is necessary to switch

from an aqueous to an organic solvent.

The water is extracted with methylene

chloride to remove any remaining organics in the aqueous phase. This methylene chloride is also used for further

Soxhlet extraction of the sediment (20

hrs) . The organic extracts are combined,

reduced to dryness by vacuum distillation and taken up in n-pentane for gas

chromatographic analysis. The solid

residue in the Soxhlet thimble is used

for dry weight determination.

The 6 cm. TENAX column from out- gassing is installed as a pre-column

to the analytical column in the gas

chromatograph (GC) . A heating block

is clamped around the pre-column and

heated to 400°C with carrier gas flowing.

Just prior to and during this flashing

operation, a stream of liquid nitrogen

is directed at the head of the analytical

column, thus thermally focusing the sam- ple on the GC column. The oven is tem- perature programmed and data are acquired

by an on-line computer throughout the course of the gas chromatogram. Data

reduction routines are available for

determining elution time and peak size.

Identification of the components trapped

on TENAX will be accomplished with a gas chromatograph-mass spectrometer

system.

The analytical columns used in the

gas chromatograph are glass SCOT columns

100 m in length x 0.76 mm i.d., drawn

and coated in this laboratory. They are coated with SE-30 on Silanox 6-lOy silica

particles. The columns exhibit more than

100,000 theoretical plates.

The analytical scheme under investigation for tissue samples is similar

to the method described above. Prior to the outgassing, an ultrasonic probe is

introduced into the extraction flask

through a normally stoppered neck and

the cell structure is disrupted. Since

no solid mass remains, the analytical

procedure is not carried beyond the

outgassing stage.

Results and Discussion - As men- tioned above, for tissue samples only the

outgassing step is envisioned. Results

of sediment studies show that aromatic

hydrocarbons such as pyrene (molecular

weight 202) can be outgassed. This

result indicates that also for sediments

Soxhlet extraction may not be necessary.

Typical chromatograms for outgassed

sediment samples from two of the sampling sites in Prince William Sound are shown in figure 2. The Dayville mud

flats (clay-type sediment) are located

across the channel from Port Valdez at the head of the Prince William Sound, in

reasonably confined waters. Hinchinbrook

Island (sandy sediment) , on the other

hand, is located outside the Valdez arm

at the entrance of the Sound into the

Pacific Ocean, and hence its beaches

are constantly washed with new ocean

water. Peak 1 is pentane, the solvent

for the internal standard. Peaks 2, 3,

4, and 5 are the components of the internal standard, each added at the 10 ppb

level based on sediment wet weight. As can be seen (Dayville sediment), pentane,

due to its great volatility, is difficult

to retain on TENAX. The Hinchinbrook

sediment, as might be expected, is much

cleaner than that of Dayville.

The advantages of the outgassing

and trapping technique for sample analysis over the more classical solvent

extraction and column chromatography

techniques are considerable:

1) There is an absolute minimum

of sample handling.

2) Separation is in a closed

system minimizing both the

risk of losses of trace

level volatile constituents

and the possibility of con- tamination by laboratory

vapors and particulates.

3) The method affords efficient

separation and concentration

of the constituents of interest.

4) Only water is added to the

198
DAYVILLE

SEDIMENT

X

HINCHINBROOK

SEDIMENT

Figure 2. Gas chromatograms of outgassed sediment samples from Dayville Mud Flats and

Hinchinbrook Island, Prince William Sound, Alaska. Peaks 1 through 5 are due to the internal standard and correspond to: CI) n-pentane, (2) mesitylene, (3) naphthalene, (4) ethylnaphthalene , (5) n-propylnaphthalene.

sample - water can be purified to a higher degree of

purity and much more readily

than organic solvents.

5) The sample ends up in a form

which can be readily chromatographed, free of large

amounts of solvents and free

of septum bleed.

6) Even reasonably nonvolatile

hydrocarbons, such as pyrene

(molecular weight 202) and

docosane (molecular weight

310) can be outgassed.

References :

[1] Bruce, H.E., Sampling Marine Organisms and Sediment for High Precision

Gas Chromatographic Analysis of

Aromatic Hydrocarbons , in Proceedings of the Marine Pollution Monitoring (Petroleum) Symposium and

Workshop, May 13-17, 1974.

[2] XAD-2, a product of Rohm and Haas

Company, Philadelphia, Pa. XAD-2

is a copolymer of polystyrenedivinylbenzene

.

[3] TENAX'^ - GC is a registered trademark of Enka N.V. The Netherlands.

Tenax GC is a porous packing material based on 2 , 6, diphenyl-p-phenyleneoxide

.

Key Words: trace analysis, hydrocarbons,

aromatic hydrocarbons, chemical baseline,

gas chromatography. Prince William Sound.

Identification of any commercial product

does not imply recommendation or endorsement by the National Bureau of Standards,

nor does it imply that the material or equipment identified is necessarily the

best available for the purpose.

199

HBS Spec. Fubl. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

LONG TERM WEATHERING CHARACTERISTICS

OF IRANIAN CRUDE OIL: THE WRECK

OF THE "NORTHERN GULF"

D. W. Mayo, D. J. Donovan and L. Jiang

Department of Chemistry

Bowdoin College

Brunswick, Maine 04011

and

Robert L. Dow and John W. Hurst, Jr. Maine Department of Marine Resources

Augusta, Maine 04330

On November 25, 1963, the Liberian

tanker Northern Gulf ran aground on West

Cod Ledge, Casco Bay, Maine, with a loss

of approximately 5,000 metric tons of

Iranian crude oil. The weather was clear;

northwest winds averaged 17.6 km. per

hour, with a peak gust of 46.4 km. [1]

Much of the oil was rafted eastward

by an anomalous clockwise eddy [2] to the

vicinity of lower Penobscot Bay where a southeast gale on November 30 drove the

oil ashore along more than 64 km. of

coast. The beach area occupied by the

stranded oil between extreme low tide and

above mean high tide was estimated to be

approximately 1.6 km^.

All commercial shellfish growing

sites, principally soft clam ( Mya

arenaria )

, were contaminated by the oil.

One regularly sampled soft clam growing

area could not be harvested for a period

of two years following the spill. In this period the supply of marketable

clams from the affected areas declined

20 percent, or 60 metric tons of edible

meats, as contrasted with an increase of

249 percent or 157 tons in adjacent

uncontaminated control areas. Most of

the loss was caused by unpalatable oily

flavor apparently imparted by repeated

or continuous recontamination by oil

entrapped in bottom sediments. Following

the immediate toxic effects [3] the

persistence of the Iranian crude oil

entrapped in bottom sediments would

appear to have played a significant but

not exclusive role in the continuing

mortalities observed in these areas during the subsequent two-year period.

These results are in contrast to the

virtually instantaneous mortalities

associated with some fuel oil spills

observed elsewhere on the Maine coast. [4]

The total two-year market loss of clams

from the spill is estimated to have been

between a minimum of 60 and a probable

maximum of 209 metric tons of edible meats.

Within the spill area were located

five tidal storage impoundments, con- taining approximately 647,000 lobsters

( Homarus americanus ) . The largest of the

lobster impoundments, located on Long

Island in Friendship, Maine, contained

approximately 300,000 lobsters. Immediate losses of 28,800 lobsters, weighing

15.2 metric tons, were reported by three

of the impoundment operators.

The dam enclosing the cove to create

the impoundment prevents contamination by

an outside oil spill except under

abnormal meteorological conditions.

Those conditions were satisfied as the

storm which brought the oil into the

Friendship impoundment on November 30,

1963, was reported by the U.S. Weather

Bureau to have been from the south with

an average wind velocity of 44.8 km/hr, a maximum of 76.8 km/hr, and a peak gust of

121.6 km/hr. [1] During the preceding

day, the wind had been from the southeast,

with a maximum speed of 4 9.6 kjn/hr and

a peak gust of 65.6 km/hr.

The Long Island lobster impoundment

has been checked periodically following

this initial contamination for visible

evidence of oil residues. It is located

in a rather isolated area which has not

been exposed to subsequent spills. On

surficial intertidal fine sediments,

however, oil still persists as a visible

sheen and in subsurface sediments as entrapped residues, with a strong oily

odor when samples of sediments and of

soft clams are collected.

As there had been no recorded

evidence of either prior or subsequent

contamination of this area by petroleum

hydrocarbons, a study was commenced

during the summer of 1972 to establish

the present state of the hydrocarbon

residues in the sediments and marine life

of this area resulting from the wreck of

the Northern Gulf . The hydrocarbon

content of the area was assayed by gas

chromatography employing a Perkin-Elmer

model 900 instrument equipped with a SCOT 50' OV-1 column. Generalized

parameters for instrument operation are given in reference [5]. Sampling

procedures for sediments and organisms

were essentially those outlined by

Blumer. [6] The resolution capability

of the OV-1 open tubular columns will

allow (with careful handling) nearly

total separations of the acyclic

isoprenoid series from Cj^^ to C2Q while

at the same time giving complete separation of all the linear chain compounds.

This result is observed in figure 1 (sample C-1) where the gas chromatogram

of the original unweathered Agha Jari

crude carried by the Northern Gulf is

shown. Of particular interest was an area in the northwest corner of the

201
pound where deep penetration of fine

sediments had occurred nearly ten years

prior to the start of current studies.

Samples Al and A2 (fig. 1)

collected in June of 1972 and March of

1973 possessed particularly interesting

chromatograms . Both samples were subsurface and were essentially devoid of

linear chain hydrocarbons (traces present

in A2). The branched chain series still

persists in these hydrocarbon residues.

With the exception of pristane the same relative abundance of C^^^ through

isoprenoids is observed (see Table I.)

Table I. Ratios of Isoprenoids

Relative to Phytane

Iranian Friendship

Isoprenoid Crude Sediments

Sample

Al(72) A2 (73) A9(74)

^4 0 8 0 3 0 3 0 2

'^IS

0 8 0 7 0 7 0 5 ^6 1 2 1 2 1 3 1 2 ^7 0 7 0 6 0 5 0 7

^18 1 0 1 0

1 0 0 9

^19 1 0 1 8 1 7 1 9

^20 1 00 1 00 1 00 1 00

with respect to the unweathered Agha Jari

crude. In the unweathered oil the C^g

member occurs in highest concentration,

whereas in the sediments pristane

dominates the isoprenoid fraction. It would appear that during the weathering

of the crude oil pristane is being

degraded much more slowly than the six

other members of this series. An

alternative explanation is that pristane

is being incorporated into the residues

from the natural environment. Substantial evidence has been found to support

the latter contention. Indeed, it would

seem that sediments located within

lobster impoundments may tend to exhibit

unusually high natural pristane concentrations. This conclusion arises from

the observation that in assaying lobsters

for hydrocarbon contamination all control

animals without exception possessed

pristane as the single dominant hydrocarbon (see sample B3a, fig. 2). Thus,

in a pound containing over 300,000

lobsters/year and with a storage mortality of approximately 5 to 81 it would be

anticipated that rather high natural

pristane levels would develop over a period of years. Indeed, in the northeast corner of the pound in surface

sediments which contained significant

contamination but which were more highly

weathered so that the isoprenoid series was reduced to trace quantities, the

single exception was pristane which was again the dominant hydrocarbon (see

sample A6 , fig. 2). Even in clams

collected within the pound pristane is

the dominant saturated hydrocarbon

(see sample B2 , fig. 2).

Thus, by correlating the relative

abundance of the isoprenoid substances

we may conclude with reasonable confidence

that the hydrocarbon residues which still

are present in the impounded area eleven

years following the spill can be traced

to the Northern Gulf . Background distributions of

hydrocarbons from sediments adjacent to the impounded area are given in figure 3. Subsurface beach sediments collected

south of the pound (sample A7) still

show moderate contamination of heavily

weathered material. Sediments obtained

from a fresh water bog draining into the

pound but not contaminated during the

spill exhibit a rich distribution of

natural hydrocarbons but no indication

of petroleum residues (see fig. 3,

sample AS)

.

Organisms living in the area also

reflect the presence of these residues.

A sample of fucus collected during July

of 1973 possessed lower concentrations,

but the same isoprenoid distribution

(sample Dl, see figure 4). Heavy concen- tration of aromatic residues in this

plant also appears to have taken place.

Clams surviving in the northwest

corner of the pound possess a hydrocarbon

distribution essentially identical to the

sediments in which they were found

(sample B4 , see fig. 4).

The clams occupying this area of

the pound are stunted, requiring eight

or more growing seasons to reach the

minimum commercially acceptable size of

approximately 45 mm long diameter. By

comparison the most rapidly growing

clams in Maine will reach market size in

three growing seasons and the coastwide

average is five.

Although water circulation is

inadequate in this portion of the

impoundment for good growth, it is

probably less important than the chronic

effects of the high level of petroleum

hydrocarbons in the sediments where

the clams live. Estimated annual linear

growth has averaged 5.6 mm with a range

from 3.6 to 8.2 mm. Although represen202
tation in the samples was limited to approximately eight year classes, nearly

four percent of the residual population

in 1973 had apparently been spawned

during the summer preceding the spill.

To evaluate further the effects

of oil residues on clams, two clamtransplanting experiments were conducted.

On June 20, 1973, 1,805 soft shell clams

ranging in long diameter from 44 to 89 mm were planted behind the dam of the

Long Island impoundment on the Northwest

shore. It was estimated that the area included in the planting consisted of

approximately 35 m^. 2032 similar size

clams were replanted as controls in

the Spurwink River, Scarboro, Maine,

using the handle of a clam hoe to create artificial burrows. The

Scarboro control area contained approximately 24 m^ of sand-silt sediments.

Nine hundred of the clams used

in the Friendship planting were inserted approximately one-half the

length of their shells in the sediments in normal growing position. The

remaining 90S clams were placed in

normal position in burrows excavated

in the sediments by means of a garden

trowel. Since these two lots were not

placed in the same portion of the study

plot, it was possible to differentiate

them geographically.

When the first recovery sampling

was made on July 23, all of the clams

which had been partially inserted in

the sediments were dead. Continuing

survival of the remaining 905 is shown

in Table II. At the time of the

November 9 sampling, 142 days following

the transplant, only two clams survived.

The total mortality for this experiment

was 87.4 percent in contrast to a total mortality of 13 percent in the

control area when that experiment was terminated on October 22, 1973.

Only 319, both living and dead,

of the 905 clams placed in excavated

burrows were recovered, suggesting that

the remaining 586 may have surfaced and

died as occurred at Searsport, Maine,

in March 1971 when a spill of #2

fuel oil mixed with JP5 killed approximately four and one-half million

commercial size clams in less than two

weeks. [4]

The surface of the experimental

area in the Friendship lobster pound

was littered with the empty shells of

those transplanted clams that failed

to burrow to their normal depth and

those which, it is presumed, surfaced

from their excavated burrows.

A second experimental transplantation of three hundred rapidly

growing 30 mm diameter clams from

Ogunquit, Maine, was made at Friendship

on August 23, 1973. These animals were implanted in the oil -contaminated

sediments at normal depth and in

normal growing position. When the

first recovery collection was made on September 21, only four living clams

could be found. The mortality rate

for the 29-day period was 99 percent,

while in the control area the mortality

during the same period was 40 percent.

Hydrocarbon sampling of the

transplants and controls indicated

that there was a rapid absorption of

hydrocarbon residues by the surviving

animals at Friendship [see Table III).

Table II.Date Number Date

Place Planted Planted Collected

Friendship June 20 1805* July 23

Aug. 23

Sept. 21 Nov. 9 Scarboro June 18 2032 July 16

(Control) Aug. 23

Sept. 20

Oct. 22

Number Number Number Percent

Collected Alive Dead Survival

93 75 18 80.6

94 75 19 79.8

111 75 36 67.6

21 2 19 9.5

83 75 8 90.4

82 75 7 85.3

83 75 8 90.4

96 75 21 78.1

*Nine hundred clams failed to reestablish themselves in burrows and were dead when the experimental area was checked on July 23, 1973.

203
Table III. Hydrocarbon Uptake by Transplanted Clams

Code # Description of Sample Date Collected PPM - Total HCs

OTP-B-1 Marked clams from Spurwink- 6/17/73 12 standard sample on day of

collection

.

OTP-B-4 Spurwink transplants used 7/23/73 8 as standard at Spurwink.

OTP-B-12 Same as OTP-B-4 8/23/73 2 OTP-B-14 Same as OTP-B-4 9/21/73 3 OTP-B-2 Spurwink transplants from 7/23/73 64

Friendship (inside lobster

pound- -northwest shore)

OTP-B-6 Same as OTP-B-2 8/23/73 88 OTP-B-10 Same as OTP-B-2 9/21/73 81

References

[1] "Local Cliraatological Data." U.S.

Dept. of Commerce, Weather Bureau,

Portland, Maine. November 1963.

[2] "Coastal Currents of the Western

Gulf of Maine," Joseph J. Graham,

International Commission for the

Northwest Atlantic Fisheries,

Research Bulletin, #7, 1970.

[3] M. Blumer and J. Sass. Unpublished

manuscript, reference 72-19, Woods

Hole Oceanographic Institution

1972.

[4] "Final Report, Searsport Oil Spill

Survey," Department of Sea and

Shore Fisheries, Augusta, Maine

1972.

[5] Injection block temperature 200°C;

Detector: Flame Ionization (400°C);

Carrier Gas: Helium, flow rate

70 second methane retention time;

Initial temperature 70°C; Final

temperature 255°C with a 24 minute

hold; programmed temperature at 6°/

minute, recorder speed 18 inches/hr.

[6] Blumer, M.G. Sonza and J. Sass,

Hydrocarbon Pollution of Edible

Shellfish by an Oil Spill,

Reference No. 70-1, Woods Hole

Oceanographic Institution, 1970.

Key Words: Oil Pollution; Gas Chromatography, SCOT Columns, Isoprenoids,

Weathered Oil, Oil Absorption,

Organisms, Sediments

204
FIGURE 1

Frlenilshln rl

Agha Jirl Crude fron Northern Culf

205
FIGURE. 2
207
i

• FIGQBE 4
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, May 13-17, 1974 (Issued December 1974).

ANALYTICAL TECHNIQUES FOR ISOLATING AND QUANTIFYING PETROLEUM PARAFFIN HYDROCARBONS

IN MARINE ORGANISMS

R. C. Clark, Jr., and J. S. Finley

National Marine Fisheries Service

Northwest Fisheries Center

2725 Montlake Boulevard East

Seattle, WA 98112 U.S.A.

Straight-chain saturated hydrocarbons (normal

paraffins or n-alkanes, CnH2n+2) are one of the major components of petroleum and of its refined

products as well as being minor but ubiquitous

compounds in the aquatic environment. They occur

in aquatic organisms, in sediments, and in sea water itself. Since these compounds can be

readily separated using liquid-solid chromatography and easily identified by gas-liquid

chromatography, normal paraffin hydrocarbons can

be used as tracers or indicator compounds for

petroletom pollution.

Normal-paraffin hydrocarbon patterns in petroleum-contaminated marine organisms can be distinguished from those of biogenic origin

within the same organisms by means of specific

analytical techniques. Benzene-methanol solvent

extraction, silica gel-alumina column chromatography, and linear programmed-temperature gas chromatography are used to isolate and identify

individual n-paraffin hydrocarbons at the nanogram

(10-9 g) level over the molecular range from 14 to

37 carbon atoms. Peak area quantification can provide a method for the preparation of n-paraffin

hydrocarbon data to indicate (1) whether petroleum

hydrocarbons have been taken up by marine organisms, and (2) to what extent this is the case. The applicability of these techniques has become

evident from the results of several hundred

analyses involving nearly 100 different types of plant, animal, petroleum, water, and sediment

samples collected under conditions of low,

moderate, and high level petrolexuti pollution.

Procedures to Isolate and Identify Paraffin

Hydrocarbons

There are four basic phases in the isolation

and Identification of paraffin hydrocarbons in aquatic organisms:

(1) preparation of samples in a non- contaminating manner;

(2) solvent extraction of the organic matter

from the cellular matrix of the samples;

(3) separation of paraffin hydrocarbons from

the extractable organic matter by chromat- ography ; and

(4) identification of the paraffin hydrocarbons by gas chromatography.

Specific details of the procedures used have

been dftscribed [l] and its application to a

niimber of petroleum-polluted and control intertldal organisms have been presented C2],[3],C4].

A flow diagram of analysis of paraffin hydrocarbons in marine organisms is given in figure 1.

Techniques for Interpretation of Data

Since the methods of hydrocarbon analysis of biological samples are relatively new, the procedures for making the data meaningful are in a developmental stage.

Once the organisms have been sampled and analyzed and the gas chromatograms obtained, it becomes necessary to interpret the results by

preparing paraffin hydrocarbon patterns for each

sample. Further calculations of parameters from

the quantitative data can be made. A number of these parameters which by themselves imply pollution, can, in combination, delineate the extent

of petroleum pollution in aquatic organisms.

Finally, when sufficient basic information has been established (baseline patterns, bioassay

uptake patterns, control patterns, etc.) in the form of paraffin hydrocarbon patterns and calculated parameters, then it becomes possible

to apply this data for the detection and following

of the uptake of petroleum hydrocarbons by marine

organisms.

Paraffin Hydrocarbon Patterns

Regardless of the gas chromatograph used, the paraffin hydrocarbon pattern is depicted as a series of spikes on a potentiometric strip chart recorder (fig. 2). The resulting "chromatogram"

from the recorder is qualitative, but it requires

further Interpretation to become quantitative.

If one assumes that the area under the individual

paraffin peak is directly related to concentration,

the absolute weight value (expressed as nanograms)

can be obtained using the proper calibration solutions, solvent blanks, dilution factors and peak

area quantification. The division of this weight

value by the "dry extracted weight" (sum of the solvent extrac tables and the "dry residue" weights),

results in a "parts-per-billion" value which can

be plotted on semi -logarithmic graph paper, against

the number of carbon atoms per molecule along the abscissa in the form of a smooth line graph

(fig. 3) for easy comparison of several patterns

or "fingerprints" on a single chart.

Calculation of Parameters

There are several parameters which can be calculated from the quantitative data obtained

during the preparatioii of paraffin hydrocarbon

patterns. As parameters that can be used to indicate petroleum pollutant uptake in aquatic

organisms, the solvent extractables , the total normal paraffin hydrocarbon content, the pristane content and n-Cl7/pristane ratio, the magnitude of the major hydrocarbon, the n-C^g ratio, the carbon

preference indices (CPI's) and the unresolved

peaks envelope are useful to varying degrees.

Application of Data

The first indication of petroleum being taken

up in aquatic organisms can often be seen in the gas chromatogram of the sample. If each of the n-paraffin peaks in the range C-^^ 22 °^ same order of magnitude, and if there is a large

209
I Jollection of Smplo j

preservation of SuDple

I

Solvjnt *nd Reapent purlfloptlon

I Proparatlon ol' Sacple

I

p*iolf or Out) HoBO.-cnizod

Soxhlot sxtraotion

(i.t .J. hr - 111 M8thftnol/?eniene)

Shell or Other un-

£:xtraoted Realdue

Air^Diy

SHELL V/EIQOT

(Jioao^tnizo J

L«nzeno ~ T~* {:!iniBUE voluae)

Larre Separstcry Funnel

Rinae Soxhlel

\ppar&tui

ShsJie and Separate

^ Inaol'ubie i^eBldue|

Air' Dry

I Welsh

1

,

Orcanle Phase

1

(Ll* 3ep. Funnel))

Aqueous Phuse

(Saall Sep, Pun .el' phaael jOr^anio Phaaa^

IC =1 pentane

I Aquaoua

I

' j' Liaoard

I Organic Phaeej

Anhydrous T Sodiuc Sulfate

Dilution Foctor: Fucus tp. t 5 Fuel Oil 6,300

Figure 2. Gas chromatogram of extracts from an alga ( Fucus sp.) and a petroleum product (#5 fuel oil). Sample size adjusted to show minimum attenuation for graphic presentation;

the petroleum pattern represents a dilution

of 1/6300 times that of the alga pattern.

Svaporate to-- 5 i=l

Tranal'er to ?ared f Container

Braporato to 'I«ar Constant "./oijht tv.' rzfi

ChroDAtograpl^ Siliea ^el/Aluaina

(5. w/w water)

aiolofieal (Soxhlot)

Petroleui

(Direct)

Pentane Blnae

t :?ed Volux^B

Precut

(Coluon Blank]

saVEi: EXTRACTASLi- (0*1 - 1.0 e)

Pentane

cut ,^1 (Para:fln fj/drocorbona)

Evaporate

Trtnafer to vial

I Dr' under yltrofeu

b'vap|rata

Transfer

I Trfelgh

1 cut !fS. 1 1 3ut rJl

Hvaplrate Svapirate

Tranifer Tranifer

1 T1 nr.:

Weigh Weigh

l3olld >li«»n [Liquid Ph«^ ja'drocarbonl I ProoJtl \oi>l ^\ |cut M fcut^TI

aVKl'"^f<^° I I

I I 1 Paok Column

I Condition Coluan

"on-Poiar Column

(nTV-502)

Quantify

(PeaJe Areaa)

Calculate

(Coaputor)

Internal Standarde

Polar Column

(csof:)

Jiantlf;.- (Poak Aroai

Plot I IKDKOCASBC!; PATTEBia

I

ppb va carbon

BtOBii7[:'Oleoul0

Conpariaon with

Other Pattern*

takufale

tttDBOCAHBc:: cj!i;:;i

DoterElne PRISTANE L

Rooaloulota n-Cw,

PrlBtane and~P>vtan'e

n-Oj( (nononreiDa) n-Oj (ppb) Total Hydrooarbona (Ci.'i^xt)

:Pi>o-j6

n-Ojg Ratio Unraaolved Puak ^velopo

Figure 1. Flow diagram of analysis of paraffin

hydrocarbons In marine organisms.

23

H o

K O OH

O S

a. a.

a. a.

in i 5°

<

(9E

O

I0,000-|

5,000

2,000

1,000

500 H

200

100

50-

20-

10-

5-

2

-

I

o Fjcua ap.

> No. 5 Fuel Oil (AgedZShrs)

10 14 18 22 26 30 34 38 CARBON ATOMS / MOLECULE

Figure 3. Line graph used for comparing paraffin

hydrocarbon patterns. An alga ( Fucus sp.

)

with its saw-toothed odd-carbon pattern

representative of biogenic samples is compared

with a #5 fuel oil which displays the smooth pattern found in petroleum samples.

210
unresolved peak envelope below the discrete

paraffin peaks, a strong probability exists that

the sample Is contaminated with a petroleum

pollutant.

The next step in establishing the levels of petroleum pollution uptake is then the converting

of the peak areas from the gas chromatogram to the "ppb-dry extracted weight" value for each

ti-paraffin hydrocarbon and replotting (fig. 3).

If the resulting pattern and content is indicative

of petroleum contamination when compared with

patterns of uncontaminated organisms and of petroleum materials, further reduction of the data is suggested.

As a start to using normal paraffin hydrocarbon baseline data obtained by the techniques

outlined above, the following sequence might be considered:

(1) obtain a gas chromatogram at maximum

sensitivity;

(2) reduce gas chromatogram peak data to "ppb-dry extracted weight";

(3) plot the "ppb" Information on semi-log paper ("fingerprint");

(4) compare "fingerprints" of suspected

organisms with unexposed controls and with petroleum;

(5) calculate: solvent extractables

total normal paraffin

hydrocarbons

H-Ciy/pristane ratio CPI14-20

^^^120-36 unresolved peak envelope

ratios;

(6) calculate "residual" hydrocarbon patterns

by subtracting the unexposed control

patterns from the suspected or exposed

patterns—positive "residual" patterns

in the shape of the pollutant pattern

Indicate hydrocarbon uptake;

(7) compare the above calculations for trends

and for an estimate of petroleum pollution.

As an example, the n;-paraffin hydrocarbon

patterns of an alga and a refined petroleum product obtained as gas chromatograms (fig. 2) are presented in PPB-Dry Extracted Weight pattern

(fig. 3) and summarized in table I. Application

of these techniques to other organisms and to various pollution exposures have been reported

[2], [3], [6].

Table I. Parameters calculated from

ii-paraffin hydrocarbon data for Fucus sp. and for a #5 fuel oil. Data from figure 3.

Parameter Fucus sp. Solvent extractables (ppm) 54,000

Total paraffin hydro- 7.217 carbons (ppm)

n-Cij/ pristane ratio 3,100

Major paraffin hydrocarbon C^^ 79.47o n-CiQ ratio 4,600

CPIi4_20 315 CPI2O-36 Unresolved peak envelope 35.8

C17 peak/Ci7_i8 tangent

#5 fuel oil

1007, 29,057

1.8 C.„12.9%

8.8

0.9

1.0

1.8

Recovery of Added Hydrocarbons

The addition of n-parafflns tc wet mussel

tissue prior to extraction was used to determine

the recovery of hydrocarbons by our techniques.

The lowest concentration of n-parafflns added was

twice the average biogenic level found in uncon- taminated mussels [3] and the highest spike added represented a maximum likely to be present in mussels directly exposed to oil in bioassay

experiments [5], [6]. The recoveries of n-paraffln

from mussel tissue added at three concentration

levels are plotted in figure 4 and summarized in table 2. These values reflect the recovery of pure ti-paraffin hydrocarbons added to the wet

tissue and do not directly establish extraction

efficiency of intracellular hydrocarbons.

Table II. Recovery of n-paraffin hydrocarbons from mussel tissue ( Mytllus edulls ) added

at three concentration levels.

Level I Level II Level III Spiked Solvent Blank

Mean added cone. a/ 0.357 tig/g 1.80 U^g/g 8.31 l^g/g 0.962 |ig -

Recovery (7.) 69.4 + 18.2 84.9 + 10.7 95.7 + 17.5 81.7 Mean +_ Std. Dev. Mean added cone. C^^_^^ 0.358 |ig/g 1.81 Hg/g 8.40 ttg/g 0.972 |Ag

Recovery (%) 92.6+20.9 92.6+9.6 99.9+17.2 86.2 Mean Std. Dev.

a/ Normal paraffins: 14, 15, 16, 18, 20, 22, 24, 28, 32, and 36; three replicate mussel samples

(4-6 individuals) analyzed at each concentration level. Concentrations in dry extracted weight,

corrected for solvent blanks; to obtain wet weight equivalents, divide by 20.9.

b/ Single determination.

c/ Recoveries expressed as mean percentage of the total of the ii-paraf fin hydrocarbons added to the sample +_ the standard deviation.

211
140

120

100

8 80

60

a. 40-

20-

Indivldual n-poroffin

o Spiked solvent blank 0.97 nQ + Mussels - Level I 0.36 pg/g dry weight Q Mussels - Level II 1. 80 pg/g dry weight A Mussels - Level III 8.31 pg/g dry weight

12 16 20 24 28 32 CARBON ATOMS/ MOLECULE

36

Figure 4. Recovery of added n-paraffin hydrocarbons from mussel tissue at three concentrations and from a spiked solvent blank.

On the basis of the evaluation of replicate

analyses of the same species of marine organisms

collected at the same location, at different

locations, and at different seasons, data indicate

that the reproducibility between identical samples should exceed 757o. Reproducibility as indicated

by percent standard deviation (100% x Std. Dev./

mean) for the sum of all n-paraffins (n-Ci4_37) in the triplicate analyses of unspiked mussels plus

the three levels of added standard hydrocarbons was 12.7%, 7.9%, 13.7%, and 9.2%, respectively.

Sliinmary and Conclusions:

Scientists studying petroleum pollution must

keep in mind that while normal paraffin hydrocarbons can be detected using the above chemical

procedures, analysis of paraffin hydrocarbons in organisms may not always be the best method for detecting petroleum pollution in the aquatic

environment. In cases where the petroleum pollutant is low in paraffin hydrocarbons (for example, some lubricating oils and even some crude oils),

other methods must be used. Under environmental

equilibrium conditions, low-level persistent

petroleum pollution may be difficult to detect

when the rate of biological degradation of n-paraffin is equivalent to the rate of pollutant

input. Further, more research is necessary to define the limits of variability of n-paraffin

analyses in aquatic populations.

Marine organisms can be used as Indicators of

petrolevun pollution when it is possible to sepa- rate the biogenic paraffin hydrocarbons from

pollution hydrocarbons. Once these paraffin

hydrocarbon methods suggest petroleum contamination of a marine population, then other methods

can be applied to delineate aromatic hydrocarbons

to establish the extent of the pollution in the marine environment.

References:

[l] Clark, R. C. , Jr., and Finley, J. S., Techniques for analysis of paraffin hydrocarbons and for interpretation of data to assess oil spill effects in aquatic organisms, in Proceedings of the 1973 Joint

Conference on Prevention and Control of

Oil Spills , pp. 161-172, American Petrolexm

Institute, Washington, D.C. (1973).

[2] Clark, R. C. , Jr., Finley, J. S., Patten, B. G. , Stefani, D. F. , and

DeNike, E. E. , Interagency investigation of

a persistent oil spill on the Washington

coast. Animal population studies, hydrocarbon uptake by marine organisms, and algae response following the grounding of the troopship GENERAL M. C. MEIGS, in Proceedings of the 1973 Joint Conference on Prevention and Control of Oil Spills , pp. 793-808, American Petroleum Institute,

Washington, D.C. (1973).

[3] Clark, R. C. , Jr., and Finley, J. S.

,

Mar. Poll. Bull . 4, 172-176 (1973).

[4] Clark, R. C. , Jr., Gibson, G. G. , and

Finley, J. S. , Acute effects of outboard motor effluent on two marine shellfish,

(Submitted for publication), (1974).

[5] Blaylock, J. W. , O'Keefe, P. W.

,

Roehm, J. N. , and Wildung, R. E.

,

Determination n-alkane and methylnaphthalene

compounds in shellfish, in Proceedings of

the 1973 Joint Conference on Prevention and Control of Oil Spills , pp. 173-177, American

Petroleum Institute, Washington, D.C. (1973).

[6] Clark, R. C. , Jr., and Finley, J. S.

,

Uptake and loss of petroleum hydrocarbons

by mussels ( Mytilus edulis ) in laboratory

experiments, (In preparation), (1974).

Key Words: Contamination; Gas chromatography;

Marine organisms; n-C^^ ratio; Paraffin hydrocarbon; Petrolevun pollution; Tissue analysis.

212
DBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum). Proceedings of a Symposium and Workshop held at NBS, Gaitheraburg, Maryland, May 13-17, 1974 (Issued December 1974).

DETERMINATION OF HYDROCARBONS IN MARINE ORGANISMS AND SEDIMENTS BY

THIN LAYER CHROMATOGRAPHY

L. Hunter, H. E. Guard and L. H. DiSalvo

Naval Biomedical Research LaboratoryUniversity of California, Berkeley

Naval Supply Center

Oakland, California 94625

The San Francisco Bay estuarine system

is subject to multiple inputs of petroleum

derived hydrocarbon from numerous different activities of man in the Bay area. In addition to chronic inflows which amounted

to approximately 0.4 tons per day in 1969

[1] , varying quantities of oil enter the

ecosystem through irregular accidental

spillage. Rather than attempting detailed

assays concerning specific identification

of hydrocarbons in the Bay, we have undertaken to analyze the "total hydrocarbon

burden" in organisms and sediments as potential systems indicators of pollutant

hydrocarbon levels.

Recent comparisons of hydrocarbon ana- lyses of organisms and sediments collected

at various distances from an urban source

of pollution have shown a relative in- crease in the presence of hydrocarbons [2]

[3] with increasing proximity to the source. This type of measurement is particularly promising for assays of longterm trends related to urban growth and

effectiveness of oil pollution control measures where relative broad scale mea- surements are acceptable for monitoring

purposes

.

Current research at our laboratory

investigates hydrocarbons in organisms as an integrative indicator of hydrocarbon

insult in Bay water. Surface sediments

(0-6 cm) have been analyzed as a transient

hydrocarbon storage compartment with a longer residence time than characteristic

of the organisms.

Thin- layer chromatography was the

method of choice for reasons of simplicity,

economy in instrumentation, and broad

applicability in analyses of different

sample types. Previous use of thin-layer

chromatography (TLC) has been made to check column chromatographic eluates for

the presence of contaminant lipids prior

to gravimetric determination of hydrocarbons in the eluates [2]. We have employed

a TLC method with simplified preparative

steps in an effort to obtain a rapid qualitative and semi-quantitative assay of

hydrocarbons. This methodology has been

developed in order to make broad surveys

of organisms and sediments where limited

facilities may be available in field laboratories, and where a simplified standard

method is needed for making worldwide com- parisons. Samples collected at selected

stations in San Francisco Bay were ana- lyzed and compared with results obtained

using the same or closely related organism

species or sediment samples, collected in

manifestly unpolluted waters of the northern California coast. Transfer experiments were carried out in which unpolluted

mussels were placed in Bay waters, and Bay

mussels in unpolluted waters, with changes

in hydrocarbon burden monitored as a test

of the methods.

A summary of the methodology is presented in figure 1. Tissues or sediments

are extracted using a mortar and pestle

with an equal weight of 550 C ashed magnesium sulfate and an equal volume of

similarly ashed grinding sand. The tissue

or sediment is thoroughly ground and re- peatedly extracted (with grinding) using

6-10 changes of glass-distilled hexane.

These procedures allow extraction of 30-

50 g tissue or sediment with 300-500 ml

hexane. A comparison between this method

of extraction and use of the Soxhlet

apparatus on the same sample showed no difference between these methods of ex- traction in the final TLC result. Adoption of these steps allowed for the extraction of large numbers of samples with minimal glassware requirements and low risk of

contamination. The extract was then

passed through a 30 x 150 mm column packed

with activated silica gel, and eluted with

1.5 bed volumes of glass-distilled hexane.

The extract was then concentrated to 1 ml

under vacuum. TLC plates ("Uni -plates"

,

Analtech Co., Canoga Park, Ca.) coated

with Silica Gel G and containing no organic

binders were pre-developed with chloroform

or acetone, then air-dried. The plates were spotted with 1-10 yl sample and developed using hexane.

The plates were first observed under

UV light to visualize fluorescent aromatic

compounds. They were then sprayed with

H2SO4 containing 0.251 KoCr^Oy and heated

to ca. 100 C for 1 hr and 200 C for 2 hr

to cTiar the hydrocarbon spots on the plate.

Hydrocarbons appeared in two groups on the

plate with aliphatic compounds migrating

to the upper part of the plate (Rf = 0.70-

0.86) and aromatic compounds retained at the lower end (Rf = 0.05 - 0.70). Fluorescent polynuclear aromatics were observed

with Rf values of 0.18 and 0.26, similar

to the results of Farrington and Quinn

[3] . Small amounts of polar compounds

which eluted from the cleanup column were retained at the origin.

Samples from polluted and unpolluted

waters were qualitatively compared for

presence of aliphatic, aromatic, and

213
SAMPLE

Glass distilled hexane Ashed sand

Asjje^ magnesium

Hexane

Solubles L_

silica gel chromatography

tissues, sediments

*

extraction

determination of moisture, % lipids

Hydrocarbons

_J

evaporation

thin- layer chromatography

iv .

I special cleanup !

i procedures ! 1^ .

Development fluorescence

\

densitometry

spot pattern

1

Data output: Quantitative:

fig total alkanes Mg total aromatics

Aig total hydrocarbons

Ratio aromatics/alkanes

Qualitative: Presence of fluorescent compounds

Spot pattern

Figure 1. Flow chart of methodology.

fluorescent aromatic compounds on TLC

plates as shown by figure 2. Semi-quantitative data were obtained by densitometric scanning of plates and recording

of scans using a logarithmic recorder [4]

.

Sample values were determined from standard curves obtained with known amounts

of docosane and anthracene. Determination

of the charring characteristics of individual compounds indicated for normal

saturated hydrocarbons about a 201 variation in spot density as a function of

chain length in the 5-80 pg range. The

variation observed with aromatic compounds

was larger, being within a factor of 4 in

the 5-20 Mg range. Analysis of a mixture

of saturated hydrocarbons was completed

with an average relative error of 171.

The charring characteristics of a Louisiana crude oil, a Kuwait crude oil, a #2

fuel oil, a bunker fuel, and a diesel fuel

oil indicated that analysis of these oils

relative to anthracene was accurate to within a factor of 2.

Using present methodology, the results

for complex mixtures are probably accurate

within a factor of 2, as determined by

gravimetric analysis of a mussel tissue

sample. Three replications of the ana- lysis of five mussel samples from the same station in the Bay showed technical and

sampling variation to be non-significant

at the P = 0.05 level, based on two-way

analysis of variance.

Figure 3 summarizes a number of representative values obtained in analyses of

organisms by the above methods. Included

in the figure are comparative values obtained by other workers [2] [5] using

different methods, which suggest our re- sults to be at least valid as order of

magnitude estimates. Proof of the usefulness of the method was obtained during

studies of the dynamic balance of hydrocarbons in organisms transferred from

polluted water to clean water and clean

water to polluted water. Table I lists

214
'0 J,

3 3

b

Figui'e 2. An example o£ a thin layer chromatography plate (width 5 an) comparing hydrocarbon

profiles of Mytilus samples from San Francisco

Bay (33) and from the northern California coast

(22) . The Bay sample contains an unusually large

burden of hydrocarbons in the alkane region of the plate (a) , a streak of aromatic compounds (b) , and

two regions which showed the presence of fluor- escent aromatic compounds as visualized under UV

light (c).

ORGANISM CONDITION TISSUE

SPONGE

Tethva sp. unpolluted

Qphtatisponqia sp. polluted

CRAB

Cancer antennariuy unpolluted

Cancer antennarlus polluted

STARFISH

Pisaster ochraceus unpolluted

Pisaster ochraceus polluted

CLAM^

Mercenaria mercenaria unpoHuted

polluted

SCALLOP^

Aquipecten irradians unpolluted

Aquipecten irradians polluted

entire entire

internal muscle

interna! muscle

digestive

gonadal

digestive

gonadal

entire

entire

entire

entire

P

ND

ALKANE AROMATIC

TOTAL

180 200 220 240 260 280 300 HYDROCARBONS /ig/g dry wt

Figure 3. Comparative hydrocarbon burdens of selected organisms as determined by the TLC method. ND = not detected.

215
Table I. Summarized results of hydrocarbon analyses o£ mussels using the

TLC method and transferral of organisms.

Sample Weeks Alkane Aromatic FPNA

Post-transfer Hg/g dry wt

bkg,u 9 (3) nd

bkg,p 130 (9) 154 (9) + u- p 11 230 40 + p- u 6 25 10

u-»- p 9 250 275 +

p-*- u 6 108 75 + u- p 4 169 248 +

( ) = no. of samples

FPNA = fluorescent polynuclear

aromatic compounds

bkg = background

p = polluted water, SFO Bay

u = unpolluted water, Calif, coast

nd = not detectable

summarized values from several transfer

experiments carried out during 1973.

The method described has also been

applied to sediments. In most cases the

silica gel cleanup step can be omitted due

to the relative absence of lipids in the

sediments. Results of sediment analyses

indicate that the thin layer method gave

results somewhat lower than published

standard methods for total hydrocarbons

[6] . Known amounts of Kuwait crude oil

in a sediment matrix have been determined

with an average relative error of 25%.

With further standardization, this

method appears to be of promise for hydrocarbon monitoring in the 1-1000 ppm (dry

wt) range, where littoral or nearshore

organisms or sediments are sampled.

Mytilus edul is (edible mussel) is a cosmo- politan species which may be of interest

in worldwide programs. Laboratory-reared

mussels or other test species known to be

free of petroleum hydrocarbons could be

experimentally placed at any selected

sampling site as integrative monitors of

chronic, intermittent, low-level hydrocarbon pollution where water sampling and

analysis are impractical.

Acknowledgements

We gratefully acknowledge support of

the Office of Naval Research through

contract to the University of California

#N00014-69-A-0200-1001, as well as technical assistance provided by Ms. B. Vince.

References

[1] Final Report to the State of California, San Francisco Bay-Delta Water

Quality Control Program. Kaiser

Engineers, Kaiser Center, Oakland,

Ca., p. XIX-20 and XI-7 (1969).

[2] Farrington, J. W. and Quinn, J. G.,

Estuarine and Coastal Marine Science

1, 71-79 (1973)

.

[3] Zafiriou, 0. C, Estuarine and Coastal

Marine Science I, 81-87 (1973).

[4] Dimmick, R. L., Wolochow, H. , and

Hunter, L., Naval Biomedical Research

Laboratory, Tech. Prog. Rep. No. 48,

U. Calif. Berkeley, pp. 161-163 (1973).

[5] Blumer, M. , Souza, G. and Sass, J. Marine Biology 5, 195-202 (1972).

[6] American Public Health Association.

Standard Methods for the Examination

of Water and Wastewater . 13th Ed .

,

A.P.H.A., Washington, D.C. (1971).

Keywords: Hydrocarbon profile; tissue

hydrocarbons; sediment hydrocarbons, hydrocarbon monitors; San Francisco Bay hydrocarbons .

216
DBS Spec. Fubl. A09, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburs, Maryland, May 13-17, 1974 (Issued December 1974).

DETERMINATION OF EXTRACTABLE ORGANIC MATERIAL AND ANALYSIS OF HYDROCARBON

TYPES IN LAKE AND COASTAL SEDIMENTS

J. W. Blaylock, R. M. Bean and R. E. Wildung

Ecosystems Department

Batten e. Pacific Northwest Laboratories

Richland, WA 99352

Marine and freshwater sediments can provide

a wealth of information relating to the ecological impact of industrial and domestic development.

In contrast to samples of water and biota, the sediments can be considered to be reflective of

local environmental conditions over a finite

period of time.

A number of analytical methods have been published which provide qualitative, semiquantitative and quantitative estimates of sedi- ment organic components. Clark and Blumer [1]

reported a method utilizing solvent extraction,

column cleanup and analysis of n-alkanes by gas chromatography. Mark and Yu [2] reported data obtained by direct infrared analysis of sediments. These methods are useful for rapid

screening of sediment organic fractions but do not provide sufficient fractionation of organic

extracts necessary for more detailed characterization of compound types.

Koons and Monaghan [3] reported a method

for extraction and gravimetric analyses of organic materials in drill core samples. The

method involved fractionation of total extractable organics into asphaltene and asphaltene-free

organic extracts which were further subdivided by

liquid chromatography into saturates, aromatics

and polar compounds. This method has been adapted in the present studies for fractionation

of marine and freshwater sediments. The saturate

and aromatic fractions were further characterized

as to compound type by application of highvoltage, mass-spectrometric techniques.

Sediment Extraction Procedure

Sediment cores, frozen iimiediately upon sampling, were divided into vertical segments

and the surface (0-5 cm) segment were freeze- dried for a minimum of 24 hours. This procedure

served to reduce the potential for biodegradation

of hydrocarbons in the sediment prior to analysis.

The dried sediment (10-50 g) was placed in a pyrex thimble with a coarse, fritted-glass

filter and Soxhlet extracted with 500 ml of a constant boiling mixture of benzene and methanol

for 16 hours. Extraction for longer periods did

not significantly increase the quantity of

material extracted.

The organic extract was evaporated to dryness under a stream of nitrogen at SO'C,

redissolved in benzene and filtered through a

glass-wool plug to remove salts. The filtrate was evaporated to dryness at room temperature and the dry-weight determined. This material was designated as the total organic extract.

Fractionation of Sediment Extract

The total organic extract was treated with

25 ml pentane for one hour to precipitate the asphaltenes. The solution, containing pentanesoluble material, was transferred to a 80 x 1 cm

column packed with 15 to 20 cm of Fisher Hyflo

Super-Cel prewashed with pentane. The column was eluted with 40 ml pentane and the eluate trans- ferred to a beaker. The eluate was concentrated

by evaporation at room temperature to approximately 5 ml, transferred to a tared aluminum

weighing pan, evaporated to dryness, and the dry

weight determined. This material was taken as the deasphaltened extract.

The residue remaining in the beaker after

removal of pentane solubles was dissolved in 10 ml benzene, transferred to the column, and eluted

with an additional 30 ml benzene. The eluate was concentrated at 60°C to approximately 5 ml , trans- ferred to a tared aluminum weighing pan, evaporated to dryness and the soluble material,

designated as benzene-soluble asphaltenes, was determined gravimetrically.

The asphaltene-free extract, dissolved in 10 ml pentane, was transferred to another 30 x 1 cm column packed with 10 g Davison Grade 923

silica gel activated at 150°C for 16 hours under

10 g Alcoa F-20 alumina activated at 400°C for

16 hours. The column was eluted with a total of

70 ml of pentane. The total eluate was concentrated, dried, and the concentration of soluble

material determined gravimetrically as previously

described for the pentane extract. This material was designated as the saturate fraction.

The column containing the residual asphaltenefree extract was eluted with 100 ml of benzene and

the concentration of soluble material in the eluate determined as previously described for the benzene extract. This material was taken as the aromatic fraction.

The column containing the remaining asphaltene-free extract was finally eluted with 100 ml of a 1:1 solution of methanol and benzene. The

material in this fraction taken to contain nitrogen, sulfur, and oxygen compounds (NSO fraction)

was determined as described for the aromatic

fraction.

Procedural Validation

The effectiveness of the procedure employed

for extraction and fractionation of petroleum

hydrocarbons from sediments was validated through recovery experiments. For these studies, a known quantity of crude oil was added to the sediment

in the extraction thimble prior to freeze-drying.

Recoveries were determined by comparison with the results obtained from analyses of oil added

directly to the solvent extraction mixture

(Table I). The minimum level (350 pg/g) was

217
Table I. Recovery of Prudhoe Bay Crude Oil from Intertidal Beach Sediment from Puget Sound'

350tig/g 675 m g/g 1340 (ig/g ASPHALTENE FREE EXTRACT 93.3 ± 2.2 107.8 ± 2.1 94.3 ± 2.4

BENZENE SOLUBLE ASPHALTENES 106.7 + 28.2 126.2 ± 29.5 76.3 ± 7.3

SATURATES 86.1 ± 2.9 110.5 ± 1.7 93.2 + 2.8

AROMATICS 121.9 + 3.3 102.0 ± 1.3 101.2 + 1.3

NSO FRACTION 94.0 ± 4.8 94.4 ± 2.9 99.9 + 4.4

^MEAN OF 3 REPLICATE ANALYSES + STANDARD ERROR; BASED ON RESULTS

OF SEDIMENT -FREE 01 L FRACTIONATION

selected from a knowledge of the background

hydrocarbon level in the sediment and the sensitivity of the procedure.

Recoveries ranged from 86 to 122% with a combined error from background and analytical losses not exceeding 5% at the low concentration level ex- cept in the case of the benzene soluble

asphaltenes. The high recoveries and large stan- dard errors reported for the benzene soluble asphaltenes is attributed to photosynthetic

pigments and other polar material occurring as background in the sediments used for these

validation studies. In general, lower standard

errors were encountered at the higher

concentrations.

Characterization of Sediment Organic Fractions

The concentrations of extractable hydrocarbons in lake sediments sampled at four locations exhibiting a wide range in hydrocarbon

contents are shown in Table II.

Table II. Gravimetric Analysis of Lake Sediment Extracts

SAMPLE DESIGNATION A B C D BENZENE SOLUBLE ASPHALTENES, ng/g 3472 2493 1558 1191 ASPHALTENE-FREE EXTRACT, aqlq . 7530 9099 1145 2234 SATURATES (% OF AFE) 24.1 2L8 17.3 10.5 AROMATICS (% OF AFE) 30.7 31.7 28.4 34.3 POLAR FRACTION (% OF AFD 29.6 28.9 28.9 16.7

Sediments A, B, and C were obtained from

locations in the vicinity of petroleum pro- duction. Sediment D was collected from an area largely free of contamination from oilproducing operations. The percentages of

saturates, aromatics, and polars (NSO) are

based on the starting weight of the asphaltenefree extract. These do not add up to 100%, a reflection of losses on the separation column

due to adsorption of polar material. Note that

sediment D is distinctive from the other three

fractions, having a lower benzene soluble

asphaltene content, and a different distribution

of component fractions in the asphaltene-free

extract.

High voltage mass spectrometric compoundtype analysis can provide detailed compositional

information on milligram quantities of sediment

fractions which would be difficult to obtain by

other means. The matrix techniques used for characterization in these studies have long been employed by the petroleum industry for routine

characterization of hydrocarbon fractions. The specific procedures used in this study were de- rived from the work of Brown, et al. [4] who

used compound-type analysis to characterize the organic material extracted from ocean waters.

The compound types determined on application of

mass spectrometric techniques to the saturate and aromatic fractions of the four lake sediments

described above are presented in Table III. The

results indicate. that the fractionation techniques resulted in good separation of aromatic and saturate hydrocarbon types, with less than 2% mono- aromatic types present in the saturate fraction.

In addition, the analysis revealed higher con- centrations of 2 and 3-ring saturates but lower concentrations of paraffins in the sediments

(A and B) containing the highest concentrations

of extractable saturates. The aromatics fractions

of samples C and D were found to contain substantial quantities of amorphous sulfur, which

interferes with the mass spectrometric method.

The use of elemental copper for removal of sulfur

from hydrocarbon fractions has been described by Blumer [5]. Application of this technique to sediment fractions prior to mass spectrometric

analysis is presently underway.

The procedures employed in the present

studies for fractionation and characterization

of the extractable organic portion of marine and freshwater sediments were well -suited to en- vironmental studies. The quantities of organic

material required for the determinations are at

218
Table III. High Voltage Mass Spectrometric

Analysis of Sediment Extracts

SAMPLE DESIGMATION

.A B C 0 SATURATES CONC. IN SEDIMENT IS 15

Aa.S. RING ANALYSIS (HOOD MATRIX)

a DAD ACCI AlC 16.5 13.0 23.1 30.8 % 1-RlNG 27.4 25.8 41.6 27.8

tL t D 1 Air 30.6 26.9 19.0 22.1 % 3"RING 22.'! 19.0 14.2 15.2 % 4 -RING 2.1 12.5 ao 3.4 % 5-RING 0.0 2.7 0.0 ao

% 6-RING 0.0 0.0 0.0 ao % MONOAROMATI CS LO 0.1 1.7 as

AROMATICS

CONC. IN SEDIMENT (iig/gl 2311 2884 325 766

M.S. ANALYSIS (HASTINGS MATRIX! % BENZENES 22.1 18.9 67.0' 2 % INDANS 12.1 18.1 13.3 HINOENES 13.2 9.2 12.9 % NAPHTHALENES 1.9 LO 2.2 HACENAPHTHENES 3.6 4.0 %ACENAPHTHALENES 8.7 7.5 UPHEN'NTrlRENES 3.7 4.7 t PYRENES 7.5 1L5 %CHRYSENES 2.3 25

4.6 » BENZOTHIOPHENES 14.1 7.4 »DIBENZOTHIOPHENES 7.5 1L2 » NAPHTHOBENZOTHIOPHENES 3.3 4.0

'about 5056 Of THE TOTAL ION INTENSITY DUE TO SULFUR.

^99*» OF THE TOTAL ION INTENSITY DUE TO SULFUR.

the milligram levels. Thus, studies of contamination in relatively unpolluted areas and in contaminated sediments are feasible. The information derived from the application of these techniques, particularly when used in conjunction with measurements of other physical and chemical properties of sediments, should assist

in determination of the relationships between

the source of environmental discharges and the sediment composition and in assessment of the environmental impact of petroleum producing

operati ons

References:

[1] Clark, R, C. and Blumer, M., Distribution

of n-paraffins in Marine Organisms and Sediment, Limnology and Oceanography 12, pp. 79-87 (1967).

[2] Mark, H. B. and Yu, T. C. Infrared Es- timation of Oil Content in Sediments in Presence of Biological Matter, Environmental Science and Technology 6,

pp. 833-834 (1972).

[3] Koons, B. and Monaghan, P. H., Data and Discussion of Analyses of the Challenger

Knoll Oil, Initial Report of the Deep Sea Drilling Project, Vol. 1, pp. 478-488

(1969).

[4] Brown, R. A., Searl , T. D., Elliott, J. J., Phillips, B. G., Brandon, D. E. and Monaghan, P. H., Distribution of Heavy

Hydrocarbons in Some Atlantic Ocean Waters,

Proceedings, Joint Conference on Prevention and Control of Oil Spills, March 13-15,

1973, Washington, D.C., American Petroleum

Institute, Washington, D.C. pp. 505-519

(1973).

[5] Blumer, M,, Removal of Elemental Sulfur from

Hydrocarbon Fractions, Anal. Chem. 29,

pp. 1039-1041 (1957).

Key Words: Aromatic hydrocarbons in sediments,

asphaltines in sediments, hydrocarbon compound

types, liquid chromatography, mass spectrometry, saturate hydrocarbons in sediments, sediment

organic extracts.

219
I

j
DBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceeding! of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

HYDROCARBONS IN BLUE MUSSELS FROM

THE KIEL BIGHT

Manfred Ehrhardt and Jurgen Heinemann

Marine Chemistry Department

Institut fur Meereskunde

an der Universitat Kiel

23 Kiel

Dusternbrooker Weg 20 W- Germany

The water of the Kiel Bight receives

relatively little obvious pollution by

fossil fuels. Occasional minor spills are

not deemed a serious problem. On the other

hand, the Baltic Sea is regarded as one of

the most heavily polluted water bodies

though mainly be excessive eutrophication.

It was an interesting question, therefore,

whether or not local shellfish contained

measurable amounts of petroleum hydrocarbons . Experimental

Blue Mussels (Mytilus edulis) were

used as test organisms in this investigation. Selected animals with shells

approximately 7 cm long were collected by

Scuba divers in April 1973 after and in

January 1974 before the spring phytoplankton bloom. The mussels were sampled from

a depth of 4 - 5 m (13 - 16 ft.) at a location east of the entrance to the Kiel

Fjord. The place is a recreation area devoid of any industry. The animals were returned alive within a few hours after

sampling and were deep-frozen immediately

after arrival at the laboratory. Work-up

began less than two weeks after collection

of the mussels. The animals are weighed

and freeze-dried without their shells. The

method has been compared experimentally

with the procedure described earlier (Blu- mer et al,, 1970; Ehrhardt, 1972; Youngblood et al., 1970). Results are the same both in terms of weight and of the chemical nature of hydrocarbons extracted from

the mussels.

Freeze-dried mussel tissue is extracted in purified Soxhlet thimbles for 24 hrs with n-pentane and for an additional

12 hrs with n-pentane + 25 percent benzene.

Column Chromatography

A column 30 mm wide is filled under

n-pentane with approximately 100 g of

deactivated silicagel (5 percent H-O) with

a bed of deactivated alumina (appro. 3 cm,

6 percent H_0) on top. The column is

washed with at least one column volume of

n-pentane. The first fraction of hydrocarbons is eluted with appro. 400 ml of

n-pentane. The first fraction is ended

immediately prior to the appearance of a yellow band of carotinoids in the eluate.

The second fraction is eluted with ZOO mi

of n-pentane. Fraction No. 3 is eluted

with 200 ml of n-pentane + 10 percent benzene.^ For a detailed analysis, fractions

No. 2 ^ (column chromatography) have been

separated on an activated silicagel TLCplate. Increasing percentages of benzene

in the n-pentane and finally pure methanol

elute polar fractions from the column

which contain the saponifiable lipids.

IR- and UV-spectra are recorded of each

fraction. Each fraction or an aliquot is

weighed on the micro-balance.

Thin Layer Chromatography

Solvent: redistilled isooctane. TLC

plate: Kieselgel 60 F 254, Merck, 20 x

20 cm. After an initial purification run

the plate is activated at 220°C for 30 minutes. Immediately after cooling the

mixture of substances is applied dissolved

in n-pentane. The separated substances are visualized under UV-light.

Gas Chromatography

Gas chromatographic separations without subsequent mass spectral analyses were carried out on a Varian Model 2740 gas

chromatograph with FID connected with a Varian A 25 strip chart recorder. The

column was 2 m x 1/16" i.d. stainless

steel packed with 3 percent Apiezon L on Chromosorb W-HP, 80-100 mesh. The carrier

gas was Helium. GC operating conditions

were the following: The injector temperature was 200 - 210°C. The column temperature was programmed from 80 - 290°C at 6°/min. Samples are dissolved in redistilled carbon disulfide.

Mass Spectrometry

For GC-MS analyses the same gas

chromatograph was operated under identical

conditions except for the column packing

and the carrier gas flow rate. The column

was 2 m X 1/16" i.d. packed with 2 percent

OV 101 on chromosorb W-HP, 80-100 mesh.

The Helium flow rate was 10.3 ml/min.

The mass spectrometer was an Atlas Varian

CH-7 with two stage Biemann-Watson separator and differential pump system. Mass

spectra were obtained under the following

conditions

electron energy: 70 eV

acceleration potential: 3000 V

beam current: 30 and 100 uA

Source temperature: 250°C

Scan: 19 linear

Amplifier: 0.1 - 1 V

Filter 3000 hz

Chart speed: 10 cm/sec

221
Results

The first batch of Mytilus was collected April 6, 1973. Upon freeze drying

the mussel tissue lost 87.0s percent of

water. The Soxhlet-extract of the dry

tissue was column chromatographed. Three

fractions were obtained, the latter two of

which were recombined to yield fraction

No. 2. Fraction No. 1 3 mg/kg of wet tissue

23 mg/kg of dry " Fraction No. 2 11.7 mg/kg of wet " 90.2 mg/kg of dry "

Gas chromatograms of fractions No. 1 and 2 are shown in Figure 1. N-heptadecane (nC,-), commonly found in many phytoplankton

species (Clark and Blumer, 1967) in benthic

algae (Youngblood et al., 1971 loc. cit.)

and in mineral oil, causes an intense peak

in the gas chromatogram of fraction No. 1. It is one of a series of normal aliphatics

beginning with n-tridecane and extending

as far as n-heneicosane towards the end of

the gas chromatogram. Pristane -2,6,10,

14-tetramethylpentadecane - (Pr) is visible

closely neighboring the n-heptadecane peak.

This branched aliphatic hydrocarbon is a common constituent of mineral oils, but is

also found quite frequently in marine or- ganisms (Avigan and Blumer, 1968). On the

other hand, phytane, 2,6,10,14-tetramethylhexadecane, which produces a shoulder at the trailing edge of the n-octadecane peak

(Ph and n-C,g) has not been found so far

as a natural component of marine organisms.

The minor siganls between the peaks of

normal aliphatics have been identified by mass spectrometry as the traces of branched

aliphatics. Mass spectrometry also reveals

the presence of alkyl - substituted mono- aromatics by intense signals at m/e 91,105,

119, 133, 147 etc. (1.11 in Figure 2). In combination, these findings confirm the

suspicion that fraction No. 1 (Column

chromatography) of the Blue Mussels collected in April 1973 is composed mainly of

petroleum hydrocarbons with a contribution

of recent biogenic hydrocarbons (e.g. n- heptadecane)

.

, ,

^ ^ .-..^J^ re

I —

i ! . :

\

'

: :

,

,

0

....

r-11

1 1

._.

.

— • M' fl

1

Fig.l: Gas chromatograms of column chromatographic fractions No.l and 2 of

Mytilus sampled in April 1973.

Fig. 2: Mass spectra of the unresolved

background of column chromatographic fractions No.l and 2 of Mytilus samples in April 1973.

The gas chromatogram of fraction No.

2 (lower of Fig. 1) appears quite different. A number of very intense signals

raise over a moderately elevated background. Mass spectra indicate C-t-C-^

mono-, di-, tri-, and tetraenes.

The background of fraction No. 2 is composed of cycloaliphatics , alkylated

benzenes, tetralenes, and naphthalenes.

A characteristic spectrum taken from the

background is shown in Fig. 2.

The second batch of Blue Mussels

collected in January 1974 at the same location has been analyzed in more detail.

Upon f reeze-drying the animal tissue lost

91.8 percent of water. Column chromatography of the Soxhlet-extract resulted in

7 fractions whose IR-spectra are depicted

in Fig. 3. From the IR-spectra it is

evident that fraction No. 1 and 2 consist

entirely of hydrocarbons. Fraction No. 3 contains traces of carbonyl compounds causing a small peak at 1740 cm" . For further

analyses fractions No. 2 and 3 were recom- bined .

222
Column chromatographic fractions No. 1 - 7

-h _LL.l ' 1

1

1 -'-

1 i

f 1 - T

r

_ .L.

-tu'. J

- —

'

;

!

1

'

-TT1"—i

:ri t

- -r —

_.+_ — 44I i - ...

1 7

,:: - [-1 , ± 1 4- !-'

- r

z -h "T" L 1 —f—

r -

1

1

3: IR spectra of 7 column chromatographic fractions of Mytilus collected in January 1974.

No.

1

2

3

4

56

7

mg/kg mg/kg

of wet tissue of dry tissue

6.16 mg 13.8

4.16 mg

0.66 mg

29.06 mg 65. 2 1397.0 mg 3135

693.8 mg 1557

49.9 mg 112

170

10.8 (No, 2+3) 133(No.2+3)

803

38591

19166

1278

total 2180.74 mg

recovery: 83.2 percent

TLC-fractions No. 2.1 - 2.4

No. mg/kg mg/kgof wet tissue of dry tissue

2.1 1.662 mg 3.7 5.6

2.2 0.845 mg 1.8 2.8

2.3 0.297 mg 0.7 1.0

2.4 0.086 mg 0.3

45.9 68.9

23.3 35.1

8.2 12.3

3.6

The gas chromatograms of fractions No. 1,

2.1, 2.2, and 2.3 are shown in Fig. 4. The numbered vertical bars mark the positions of mass spectra. A comparison with

fraction No . 1 of the batch of mussels collected in April 1973 (Fig. 1) reveals

striking differences. In fraction No. 1 of the mussels collected in January 1974

the peak intensities of normal hydrocarbons are much diminished relative to the

background and relative to pristine (Pr)

and Phytane (Ph) . The peaks of these

branched aliphatics have approximately

both gas chromatograms. The peak of one presumably recent biogenic hydrocarbon

(fraction No.l, Fig. 4) rises above all

others. The mass spectrum (2.6 in Fig. 5)

indicates a molecular weight of 344 cor- responding to the general formula ^2^^^^.

A mass spectrum of the background

positioned at 5 (2.5 in Fig. 5) shows peaks

characteristic of alkanes, cycloalkanes

(m/e 83, 97 etc.) monoaromatics (m/e 119,

133, etc.) tetralenes (m/e 145, 159, etc.),

(Ehrhardt, M. , 1972, loc. cit. and refer- ences cited therein)

.

Some characteristic mass spectra of

fractions No. 2.1, 2.2 and 2.3 are shown

in Fig. 6. The mass spectrum 2.1.3 is

characterized mainly by three fragmentation series: monoaromatics with fragments

at m/e 105, 119, 133 etc., tetralenes with

fragments at m/e 145, 159, 173 etc., and

naphthalenes with fragments at m/e 115, 141,

155. Spectrum No, 2.1.4 is characteristic

for phenylcycloparaf f ins

.

Spectrum No. 2. 1.6 shows a fragmentation series produced by hydrocarbons of

the general formula C H.-.i*, among them

alkylated biphenyls, ana of the general

formula C_H,_ denoting alkylated naphtalenes, ^ ^^'^^

223
Fig. 4: Gas chromatograms of 4 fractions

(column chromatography and TLC) of

Mytilus collected in January 1974

Uf

250 fnife360

Fig. 6: Characteristic mass spectra of TLC- fractions 2.1, 2.2 and 2.3 of Mytilus collected in January 1974.

Fig. 5: Mass spectra from fraction No . 1 of

Mytilus collected in January 1974.

Spectrum No. 2.2.5 has intense peaks

at m/e 165, 179, 193 and a corresponding

molecular ion peak at m/e 222. This series

is in good agreement with the fragmentation pattern of alkylated f lourenes . m/e

206 is the M+ -peak of a dimethylphenanthrene, and m/e 208 denotes an alkyldihydrophenanthrene . No. 2. 3. 5 is interpreted

as the mass spectrum of, primarily, a dimethylphenthrene (MG 206)

.

224
Conclusions

Blue Mussels (Mytilus edulis) from a location in the Kiel Bight, contain fossil

hydrocarbons in concentrations somewhat

above the natural background of recent

biogenic hydrocarbons. The composition of

the hydrocarbon fraction is not constant.

Mussels collected after the spring phytoplankton bloom contain relatively large

amounts of recent biogenic hydrocarbons

whose concentrations in mussels collected

in January are quite low. On the other

hand, concentrations of cycloalkanes

,

mono-, di-, and tri-aromatics as well as mixed types of fossil origin have a ten- dency to rise. The experimental results

may be interpreted as follows:

1) The mussels exchange hydrocarbons with

the surrounding water which contains

a relatively constant if not rising

concentration of fossil hydrocarbons

in addition to recent biogenic hydrocarbons whose concentrations vary

seasonally.

2) The mussels are able to degrade recent

biogenic hydrocarbons which they ingest

with their food and take up from the

water, but are much less efficient in

degrading cyclic saturated and aromatic

hydrocarbons originating from fossil

fuels.

3) Some time near the start of the experiment the mussels were exposed to oil

pollution. Subsequently, they exchange

saturated and olefinic hydrocarbons

much more rapidly with the water than

cyclic and aromatic hydrocarbons.

Present data are insufficient to decide on one of the three interpretations

given above or a combination thereof. As

a working hypothesis it is assumed that

hydrocarbons introduced as pollution and

excreeted by phytoplankton are predominantly injected at or near the sea surface.

Subsequently, they are adsorbed onto or dissolved in particulate matter, because

the partition coefficient should favour

the solution of hydrocarbons in the lipids

of detritus. Detritus then carries the adsorbed or dissolved hydrocarbons to the

seafloor where they are ingested by filterfeeding organisms.

Acknowledgement

The authors gratefully acknowledge the

generous support by the Deutsche Forschungsgemeinschaft (EH 39/7, Gr. 320/13).

References

Avigan, J., and M. Blumer (1968) The Origin

of Pristane in Marine Organisms.

J. Lipid. Res., 9, 350-352

Blumer, M. ; G. Souza and J. Sass (1970)

Hydrocarbon Pollution of edible

Shellfish by an Oil Spill.

Mar. Biol. , 5, 195-202

Clark, R. C. and M. Blumer (1967) Distribution of n-paraffins in marine

organisms and sediments.

Limnol .Oceanogr . 12^, 79-87

Ehrhardt, M. (1972) Petroleum hydrocarbons

in Oysters from Galveston Bay.

Environ. Pollut. , 3, 257-271

Youngblood, W.W. ; M. Blumer, R. L. Guillard

and F. Fiore (1971) Saturated and

unsaturated Hydrocarbons in Marine

Bethic Algae.

Mar. Biol., 8, 190-202

225

ITOPICAL SESSION V. Tar Balls and Particulate Matter: Analytical Methods

227

HBS Spec. Fubl. 409, Marine Pollution Monitoring (Petroleun), Proceedings of a Symposium and Workshop held at NBS, Galtheraborg, Maryland, May 13-17, 1974 (Issued December 1974).

IDENTIFICATION OF MINERAL 0II5 BY

FIEID IONIZATION MASS SPECTROMETRY*

M. Anbar, M. E. Scolnlck, and A. C. Scott Stanford Research Institute

Mass Spectrometry Research Center

Menlo Park, California 94025

It has been reported that crude and fuel oils may be identified through their nonfragmented mass spectra using field ionization mass spec- trometry [1,2]. Unlike conventional ^lectrSn

impact ionization (EI), field ionization (FI) of organic molecules produces virtually no ionic

fragments. Figure 1 presents the mass spectra of n-tetracosane (Cg^Hgo) by EI and FI . It is evident that FI produces only the molecular ion^.

400

(a) ELECTRON IMPACT SPECTRUM OF

n-TETRACOSANE, M.W. = 338.67

MOLECULAR ION MULTISCAN WITH

E X B FILTER

200 —r—

250 300

SCANNED BY,

MAGNETIC SECTOR

20

(b)

I 50

"~i r

100 150 ~i—I—I—r~200 250 300350 FIELD IONIZATION SPECTRUM OF

n-TETRACOSANE, M.W. ' 338.67

TA-340e83-1

Figure 2 presents a mass spectrum of four pure hydrocarbons in the mass range 255 to 311. The

molar fractions of the constituents may be compared with the total ion count of each molecular

ion. It Is evident that FI provides, in addition

to unambiguous qualitative Information, meaningful quantitative data.

^19^40 ^21^44 C22H46

26.9M% 29.2M% 32.6M%

^18*^38

1 11.3M%

L h

1 1 1 1 1 1 1 1 1 1 rrT'vi T'j

200 220 240 260 280 300 320 340 360

TA-340S83>2

FIGURE 2 FIELD IONIZATION MULTISCAN OF FOUR

PURE HYDROCARBONS

FIGURE 1

Field ionization is facilitated by the high

field gradient that can be produced at surfaces

with very high curvatures. A cathode with a radius of curvature of about 0.1 and an anode at

a distance of 75 |j, require less than 3000 V to produce field ionization. Such a configuration is readily attainable in a reproducible manner by the appropriate technology. At SRI we developed the technology for producing arrays of hundreds of microcones on a porous substrate [3] . These

arrays constitute the crucial element in our present ionization sources. They allow better

sample feed and more uniform and reproducible

operation than field ionization sources previously

used. Figure 3 shows the cross section of an operational field ionization source in which the temperature of the sample can be controlled

independently of the temperature of the source.

The ionization efficiency of our screen-mounted

ionization sources is 5 x 10~^ or higher [4], and

the Ionization efficiencies of individual components in a mixture are independent of each

other [4]. However, owing to the relatively large

area of our ionization source (about 2 mm^), the high energy of the ions produced, and their divergence, the overall efficiency of the present

generation of field ionization mass spectrometers

is only about 10"® for instruments with a magnetic

sector or a Wlen ion velocity filter, when these mass analyzers reach resolutions of 800-1000. In the analysis of crude and fuel oils, where we are

not sample limited, this sensitivity is completely

adequate. Thus 100 \ig of material, which is an adequate sample, allows us to determine with a 3% precision even components that constitute 10"* of the total mixture (when we scan over a range of 200 amu).

This work is sponsored by the U.S. Coast Guard

under Contract D0T-CG-22996-A

.

Thanks to Its nonfragmentlng nature, FI allows

the analysis of multicomponent mixtures. Each

peak In a mass spectrum of such a mixture is

a measure of the abundance of a single constituZ29
MOLYBDENUM

DECELERATION DOME

/ MULTIPOINT ARRAY

AND IONIZING GRID

ALUMINA

QUARTZ SAMPLE

PROBE

FIGURE 3

TA-339583-23 SCHEMATIC CROSS SECTION OF MULTIPOINT

IONIZER SHOWING DECELERATION LENS AND

SOLID SAMPLE PROBE

ent or of the sum of all the isomers and isobars

having the same gross molecular weight. It should be remembered that the composition of the vapor phase over a multicomponent mixture changes

as it evaporates into the ionization source, leaving the less volatile constituents behind. To achieve reproducible quantitative analysis

of multicomponent mixtures, one can integrate many rapidly scanned mass spectra of the mixture, obtained while it evaporates through the ionizing grid, into a composite mass spectrum

that represents quantitatively the composition

of the sample. The requirements in this case are that the change in composition of the vapor phase during each individual scan be minimal

and that the scanning be continued until complete

exhaustion of the sample. We have adapted the E x B Colutron ion velocity filter for a multiscannlng mode of operation.

Figure 4 is a schematic description of the instrument. The ramp voltage taken from the time base of the multiscaler is amplified after

conversion to a linear mass-time dependence to produce a changing voltage on the electrostatic

plates of the velocity filter. Figure 5 is a multiscan of a crude oil sample produced on this Instrument. The resolution of 800 obtained here

is an important achievement considering that this

is a composite spectrogram obtained from hundreds

of Individual scans.

VELOCITY VERTICAL

FILTER DEFLECTION

PLATES

ELECTRON

MULTIPLIER DETECTOR

RAMP AMP AND

TRIGGER

409G CHANNEL

MULTISCALER SPECTRUM

INTEGRATOR

MAGNETIC

TAPE STORAGE

FIGURE 4 SCHEMATIC OF FIELD IONIZATION FINGERPRINT APPARATUS

(a) INTEGRATED MASS SPECTRUM OF MID-CUT

QUIRIQUIRE VENEZUELA CRUDE OIL OVER

WIDE MASS RANGE

T

ill

ii !' ii

210 220 230 240 250 260

(b) EXPANDED SECTION

270

SA-2028-18R FIGURE 5 INTEGRATED MASS SPECTRUM OF MID-CUT

QUIRIQUIRE VENEZUELA CRUDE OIL OVER

WIDE MASS RANGE

Figure 6 presents highly expanded sections of multiscan fingerprint spectra of crude oil. This

figure is hand-drawn from the digital data printout of the multiscan spectrum.

The application of the integrated multiscan

methodology to the identification of oil slicks

is shown in Figure 7. There is no difficulty

whatsoever in distinguishing between each of the three No. 6 fuel oils, or each of the three crudes presented in Figure 8, and it also is easy to see the similarity between the repeated

spectra of the same crude oil.

230
252

1580 1600 1620 1640 1660 1680 1700 1720 CHANNEL NUMBER

TA-339525-23B

FIGURE 6 EXPANDED PLOT OF VENEZUELAN CRUDE

OIL FINGERPRINT

"T—I—'—!—

r

n—i—I—I—I—I—1

]—I—r~ BRAND A

REFINERY 1

BRAND A

REFINERY 1

iJ.LiLliLlil.,|jili,i).l'.

BRAND A

REFINERY 2

BRAND A

REFINERY 2

BRAND B

BRAND B

I I I I i i I I I 220 240 260 280 300 320 340 360 380

SA-2028-19R

FIGURE 7 FINGERPRINTS OF NO. 6 FUEL OILS

Figure 9a is an integrated multlscan spectrum of

a front cut (up to 140°C, 50 ]i) of the same fuel

oil No. 6 shown in Figure 9b. Comparing Figures 9a and 9b, it is clear why we prefer to take a mid-cut from the oil. The low molecular weight constituents may readily vary

from one sample to another because of accidental

evaporation, and the heavier fraction adds

little information while considerably increasing the analysis time before achieving complete

evaporation of the sample through the ionization source

.

—I—I—I—I—I—I—T—I—I—I—i—I—I—I I I \ I r ANNEJO-WEDIN, TEXAS

QUIRIQUIRE,

QUIRIQUIRE,

VENEZUELA

W...Ma>iM»

STATESBURG, MISSOURI

STATESBURG, MISSOURI

1 1

I I i \ I r~l \ I I I

!

\ 220 240 260 280 300 320 340 360 380

SA-2028-20R

FIGURE 8 FINGERPRINTS OF CRUDE OILS

(a) FRONT CUT

1 1 1 1 r

lb) MID-CUT

J L

100 150 200 250 300 350 400

TA-340622-4

FIGURE 9 INTEGRATED MASS SPECTRUM OF NO. 6 FUEL OIL—100°C @ 100 MICRONS AND

140°C @ 50 MICRONS

Routine identification of a sample of unknown

origin by comparison with a library of mass

spectra of known origin must be carried out by

computer analysis. Description of this methodology, which is now under development, is outside

the scope of this presentation.

In conclusion, any passive "fingerprint"

method for the identification of the origin of oil spills must be evaluated by the amount of

231
reproducible, quantitative, and characterizing

Information it provides about a given oil sample. The more quantitative information provided about

the sample, the higher the probability of positive Identification, and the lower the chances for false positives. Based on these criteria field ionization fingerprint mass spectrometry seems to surpass other competing

techniques.

Acknowledgement: The authors wish to thank

Dr. Alan P. Bentz of the U.S. Coast Guard

R and D Center for helpful discussions.

[2] Anbar, M. , Scolnlck, M.E. , and Scott, A.C.

,

Abstracts of the 1974 Pittsburgh Conference

on Analytical Chemistry and Applied . Spectroscopy (March 1974) No. 224.

[3] Spindt, C.A., J. Appl. Phys . 39, 3504 (1968);

Aberth, W.H. , Spindt, C.A. , and Sperry, R.R., Proceedings of the 21st Annual Conference

on Mass Spectrometry and Allied Topics, San Francisco (May 1973) p. 453.

[4] St. John, G.A. and Anbar, M., Proceedings of the 21st Annual Conference on Mass Spectrometry and Allied Topics, San Francisco

(May 1973) p. 139.

References

[1] Scolnlck, M.E., Scott, A.C., Aberth, W.H.

,

and Anbar, M., Proceedings of the 21st Annual Conference on Mass Spectrometry and Allied Topics, San Francisco (May 1973)

p. 345.

232
NBS Spec. Fubl. 409, Marine PolluCloa Monitoring (Petroleua), Proceedings of a Syoposlim and Workshop held at NBS, Galchersburg, Maryland, May 13-17, 1974 (Issued December 1974).

PELAGIC TAR IN THE GULF OF MEXICO

AND CARIBBEAN SEA

L. M. Jeffrey, W. E. Pequegnat, E. A. Kennedy, A. Vos and B. M. James

Department of Oceanography

Texas A&M University

College Station, Texas 77843

The Gulf of Mexico might be expected to have a relatively high pelagic tar concentration,

because it is a semi-enclosed sea with a weak

circulation in the central and -western parts and

because of its extensive offshore oil production

and tanker traffic. Since there was inadequate

information on floating tar distribution in both

the Gulf of Mexico and Caribbean, 104 samples

of floating tar were collected on cruises of Texas A&M University's R/V Alaminos and

Gyre. Half of the samples were collected with a one -meter plankton net (mesh size 240) with

floats attached to sides of the mouth of the net, so it would travel evenly in the water half submerged. The other half of the samples was

collected with a semi -quantitative neuston net, which was 2 m wide and 10 m long with a mesh

aperture of 1 mm. When attached to a 1 X 2 m

tubular aluminum frame and towed at 2 knots,

the net fished evenly to a depth of 0. 5 m. The

nets were towed for 30 to 60 minutes at an average speed of 2 knots. Area of sea surface

skimmed was 18, 500 to 37, 000 square meters.

The net contents were transferred as quantitatively as possible to glass jars and frozen. In the shore laboratory, the tar was hand-picked

from the samples, dried and weighed. Tars were then dissolved in benzene and the solution

filtered through Gelman Type A fiberglass

filters to remove the debris. The filtered solution was then evaporated to constant weight

in a circulating air oven at 50"C. The concentrations of pelagic tar expressed as mg tar/m® were calculated from the benzene -soluble dry

weight and the area towed.

The locations of the tar stations and the approximate concentrations are shown in Figure 1. Pelagic tar concentrations in the Gulf of Mexico ranged from 0 to 10 mg/m^ with an arithmetic mean concentration of 1. 20 mg/

m^. In the Caribbean, the pelagic tar concentration ranged from 0 to 4. 51 mg/m° with an

arithmetic mean of 0. 74 mg/m^. There were

84 samples for the Gulf of Mexico and 20 for the Caribbean.

Figure 1

From the available data, it appears that the

Gulf of Mexico as a whole has lower concentrations of pelagic tar than the Mediterranean Sea

and the Sargasso Sea and the Northwest Pacific

(See Table I). The Gulf of Mexico appears to have slightly more tar than the Caribbean, and

the Northwest Atlantic marginal sea and probably

about the same concentration as the Gulf Stream.

It should be pointed out that pelagic tar concentrations reported in the literature by Wong, etal.

[1], Butler, etal. [2] and Horn, etal. [3] were

obtained from wet weights and are not strictly

comparable to the data reported here. Our

results show that the non-tar particulates

amounted to an average of 36. 6% of the dry

weight with a range of 5-77% of the dry weight.

Probably, there are insufficient data in all these

marine areas to warrant any final conclusions.

Table I. Comparison of Pelagic Tar Concentrations in the Gulf of Mexico

and Caribbean with those of Other

Marine Areas

No. Range Mean Tar

Region Sanples (mg/m^) Concentrations

(mg/m^)

Gulf of Mexico*

Caribbean Sea«

Northwest

Pacific [1]

Northeast

Pacific [1]

NW Atlantic Marginal Sea [2]

Gulf Stream [2]

Sargasso Sea [2]

Mediterranean [3]

* This work

84 0-10.0 1. 20

20 0-4.5 0. 74

15 0.3-14.0 3. 8

18 0.0-2.9 0. 4

8 0.0-2.4 0. 9 16 0. 1-9.7 2. 2 34 0. i-4ao 9.4

41 0.0-540 20. 0

233
In an attempt to determine the general sources of the pelagic tars, gas chromatography,

asphaltene and sulfur analyses were determined

for 50 pelagic tars and for comparison purposes,

also on 78 beach and 13 abyssal tars dredged

from the bottom of the western Gulf of Mexico.

Gas chromatography of the tars were done

on a 6-foot, 3% SE-30 on Chromsorb P colximn

in an F and M Model 700 gas chromatograph

with a flame ionization detector. Temperature

programming from 100° to 290° at the rate of 10° /minute was used for separation of the hydrocarbons. Total sulfur percentage was

determined on the tars by combustion in a Leco

furnace and iodometric titration of the SOg

(ASTM method E30-47). Precision of + 3% of the total sulfur was obtained. The percentage

asphaltenes was determined by exposing one gram of tar at room temperature to 40 ml

pentane three times for an hour each time. The

material insoluble in pentane but soluble in benzene was the asphaltene fraction.

All the gas chromatograms of the pelagic tars had sharp spikes above the baseline with

very little humping in contrast to many beach

and abyssal tars which often had very small or no spikes and much humping. Thirty -two percent of the pelagic tars showed a bimodal distribution of peaks, which, according to Butler,

et aL [2] represent tanker sludge residues.

The remainder of the gas chromatograms

appeared to be mostly crude oils from their

carbon chain number range and distribution of hydrocarbons. No attempt was made to relate the tars to specific sources. Cg^/Cgg and C^l

Ci7 ratios were calculated when possible to determine the number of sources. It was not possible to do so with most of the beach tars and abyssal tars, because they were too weathered. The number of sources for the pelagic tars was at least 15, on the basis of gas chromatograms.

In Figure 2 it is shown that fifty percent of the pelagic tars had 1-2% sulfur, 27% had < 1%

sulfur and about 10% had > 3% sulfur. In sharp

contrast, all the abyssal tars had > 3% sulfur with a range of 3 to 8%. The sulfur content of the beach tars had a much broader range than

the pelagic or abyssal tars. From the available data on the effect of weathering on sulfur content of oils, and on the % sulfur of crudes

produced worldwide, it seems possible that at least 60% of the pelagic tars did not originate

from U- S. northern Gulf Coast oils but from

foreign crudes from the Caribbean or the Middle East. The 27% of pelagic tars with a sulfur content < 1% could possibly have originated from northern Gulf Coast oils. The

origin of the high sulfur abyssal tars could be

the remnants of oil seeps or sinking of dense,

weathered, high sulfur pelagic tars. From

their large size and lack of particulate material

in the matrix, we tend to believe the former.

The beach tars obviously had many sources, but the highest percentage contained > 2% sulfur,

which again indicates perhaps a foreign high

sulfur oil transported by ships and/or currents.

5040

3020

10

o' 50

(/>

a.S 30 <"20

ti. ° 10

^° 0

5040

30

20

100

PELAGIC TARS

( AVG. 1.50 % S)

I i I B I I - I - I I

ABYSSAL TARS

(AVG. 6.10 % S)

J L I

I

I I

B I u

BEACH TARS

(AVG. 3.53 % S) '23 I I J I 4 5 6 7 8 9 % SULFUR

Figure 2

All the tar samples contained > 5%

asphaltenes. In general, asphaltene content was highest in abyssal tars with an average of 55% ; pelagic tars had an average of 26% ; and

beach tars an average of 32. 1% as shown in Figure 3. The majority of pelagic and beach

tars were in the range of 10 to 30% asphaltene.

PELAGIC TARS

lAVG . 26 % )

i 1 1 1 1 1 1

I 30 a

ABYSSAL TARS

I AVG. 55% I jj 1 50- 40-

I

BEACH TARS

(AVG. 32.1%)

_BL__L

40

V. ASPHALTENES

Figure 3

234
In general, asphaltenes are not lost during

weathering processes, so these compositions

are dependent on the initial asphaltene content

of the oil and weathering of light compotinds.

A ntimber of northern Gulf Coast oils and light fuel oils do not form tars because they contain no asphaltenes. Percentage asphaltenes on

the environmental tars is not as diagnostic as we had hoped, so we are currently obtaining

gel permeation chromatograms on the asphaltene fractions which appears to be more

diagnostic.

In summary, the Gulf of Mexico apparently has less pelagic tar than the Mediterranean

and Sargasso Sea, but more than the Caribbean

and northeast Pacific and about the same amount

as the Gulf Stream. Some of the pelagic tar is swept into the Gulf of Mexico through the Yucatan Straits and out through Florida Straits and primarily from shipping and tanker cleaning

operations. Specific sources are difficult to ascertain on these obviously weathered materials, so a multi-parameter approach is necessary.

Other diagnostic parameters recommended for study are CHN, trace element composition of the tars and the molecular size patterns of the

asphaltene fraction. A catalog of such information is needed for many weathered crude and

fuel oils from all over the world to pinpoint

environmental "tar ball" sources. References

[1] Wong, C. S. , Green, D. R. and

Cretney, W. J. , Pelagic Tar in the Pacific

Ocean. Background Papers for a Workshop on Inputs, Fates and Effects of Petroleum in the Marine Environment,

May 21-25, 1973, v. II, pp. 400-413

(Preprint). Prepared tinder the Aegis of Ocean Affairs Board, National Academy

of Sciences, Washington, D. C. (1973).

[2] Butler, J. N. , Morris, B. F. and Sass, J., Pelagic Tar from Bermuda and the Sargasso

Sea . Bermuda Biological Station for Research Spec. Publ. no. 10, 346 pp.

(1973).

[3] Horn, M. H. , Teal, J. M. and Backus,

R. H. , Science 168, 245-246 (1970).

Key Words: Pelagic tar. Tar balls. Gulf of Mexico tar balls, Caribbean tarballs. Sulfur

of tar balls, Asphaltenes of tar balls.

235

nS Sp«c. Publ. 409, Hailni Pollution Monitoring (Potrolaua), ProcMdlnga of a Symposium and Workahop held at DBS, Caitheraburt, Maryland, May 13-17, 1974 (laauad Dacember 1974).

MARINE ENVIR0I4MENTAL MONITORING:

TRACE ELEMENTS IN PERSISTENT TAR BALL

OIL RESIDUES

Milton H. Feldman

and

David £. Cawlfield

Coastal Pollution Branch

Pacific Northwest Environmental

Research Laboratory

National Environmental Research Center

Office of Research and Development

U.S. Environmental Protection Agency

Corvallis, Oregon 97330

INTRODUCTION

The quantitative characterization of

oil pollution and residues in the sea has

been the subject of numerous investigations. Methodology choices have been

dependent on the particular goal of the

investigation. Thus, the overall descrption of the oil, or at least of the non- polar hydrocarbon chemical species in it,

has been perceived as the essence of the

problem, and has led to elaborate testing

procedures for characterization of these

materials in water, sediments, and biota.

See Figure 1, which shows some well known

procedural approaches to the analysis of

petroleum pollution of the sea, developed

by Blumer (1972), Farrington (1972), and

Levy (1973).

A significant new aspect of monitoring

of oil pollution, a persistent fraction

resulting in tar balls has been described,

and a review of the information available

has been presented (Butler 1973). Possible ecological importance of these materials has been discussed, in terms of

Trace Material Interaction of Oils and

other materials present in the surface

films and slicks on marine waters (Feldman

1973a).

Analysis of tar balls by gas chromatography (Levy 1973) actually only gets at

about half of the material. This is probably due to the high boiling character of

some of the material (Butler 1973), (Koons

(1973).

METHODS

In attempts to get a forensic system

for government regulatory procedures

against oil polluters some workers have

utilized Instrumental Neutron Activation

Analysis (INAA) as a finger printing device, (Guinn, 1970), and some have examined the weathered fraction of the petroleum for a similar purpose (Filby 1971).

Using readily procurable stock items, an automated equipment, shown in Figure 2,

utilizing computer data analysis, has been

developed, (Feldman 1973b).

After suitable irradiation and decay, a set of samples is placed in the counting

and recording system consisting of a Nuclear Chicago, Model 1085, mechanical

sample changer, which is coupled to and

controlled by a Nuclear Data 2200 Pulse

Height Analyzer (PHA) . The PHA records

signals (pulses from the 15% efficiency,

2.3% resolution, Ge(Li) crystal* in its

4096 channel memory through a SO megaherz

ADC. At the conclusion of a preset count

period the data is read out into either:

a. A telephone line feeding directly to the computer**, or

b. A magnetic tape bulk data storage

system based on Kennedy tape transport model 3112.

Routine analysis utilizes the tape; experimental development work utilizes either the

wire or the tape or both. The tape is hand

carried to the computer at the end of a sequence of samples for subsequent interrogation and printout of tables of data as allowed for in our computer programs.

All of the relatively unsophisticated

programs which allow diversity of applica- tion were each generated, as the need be- came obvious, as a convenience to allow a technician to carry out simple laboratory

procedures and to have voluminous data

handled for him as a substitute for rather

pedestrian data printing and hand computation. The program items presently available allow for:

1. Area calculation of any "regions of

interest" whose boundary channel numbers

are specified to the computer. These areas

are corrected for background, compared to standards similarly specified, and subjected to standard deviation statistical examination. This program is particularly useful for tracer experiments generating many

samples with a few radionuclides, known to be present. It is also useful for computer

interrogation where a specific nuclide is

being evaluated experimentally for procedure development.

2. Calibration of the 4096 channels of

the PHA for a range of energies by use of

a set of standard materials (Filby 1970) or more often by the use of an element like

europium-lS2 which has several well-known

gammas over the range of energies generally

Compared to a 3" Nal crystal and using a Co-60 1.33 MeV line; by the manufacturer,

EDX International, Pl-airie View, IL. **Oregon State University (OSU), Control

Data Corporation 3300 * OSS operating

system.

237
0.5 TO 20 LITERS

OF WATER

CCI^ EXTRACTION

(OTHER SOLVENTS)

UV ABSORPTION AND /OR

UV FLUORESCENCE

SPECTROMETRY- INITIAL SCREENING FOR PRESENCE

OR ABSENCE OF AROMATIC HYDROCARBONS

HYDROCARBONS AND

OTHER CCI4 EXTRACTABLE

ORGANIC COMPOUNDS

IR SPECTROMETRY

HYDROCARBONS PLUS EXTRACTABLE ORSANIC COMPOUNDS

ORAVIMETRIC- FOR IR -AS

CHANGE SOLVENT IF REQUIRED TO CCI.

LIQUID COLUMN CHROUATROGRAPHY

(SILICA GEL, ALUMINA-SILICA GEL)

NON- POLAR SOLVENTSPOLAR SOLVENTS

1 TOTAL SATURATE AROMATIC HYDROCARBONS HYDROCARBON HYDROCARBON

FRACTION FRACTION

IR SPECTROMETRY--

TOTAL HYDROCARBONS

GRAVIMETRICTOTAL HYDROCARBONS

HIGH CONCENTRATIONS ONLY

CHANGE SOLVENT

TO N-HEXANE

-MASS

UV ABSORPTION AND/OR

UV FLUORESCENCE

SPECTROMETRY— PRESENCE

OR ABSENCE OF AROMATIC HYDROCARBONS

GAS SPECTROMETRY--

HYDROCARBON TYPE

COMPOSITION, INDIVIDUAL KEY HYDROCARBONS —CHROMOTOGRAPHY— FINGER PRINT;

BOILING range; INDIVIDUAL HYDROCARBONS; ALKANES.

AROMATICS, ALKENES, HYDROCARBON

RATIOS. AMOUNT OF INFORMATION DEPENDENT UPON PRIOR HYDROCARBON

SEPARATION AND CHROMATOGRAPH

ORGANIC SULFUR COMPOUNDS WITH FLAME PHOTOMETRIC DETECTOR

Figure 1. Flow diagram for analytical techniques to measure

Cio plus hydrocarbons in waters (Levy 1973).

Nuclear Chicago 1035

Sample Chofiger

z;

CAHN ELECTRO- BALANCE

EDAX Ge(LI) I5%e

Stquencfl Control

LED READOUT

Ktnnedy Tope

Transport 3112

oooooooooo

Clock

Indoxer

Control

Switcti Canter

-0©

Paper Punch

osu

Computer CDC 3300 + OS 3

Figure 2. Schematic of automated equipment.

238
used. Comparison of any unknown peak is by

interpolation between the closest peaks

used in the calibration.

3. Peak searching by observation of

changes of slope between successive sets

of channels by the procedure of Feldman

(1973b), locates the edges of the peak,

the peak energy, estimates the area of the

peak, corrects for background, and estimates the standard deviation of the area. Printout of this information comprises the

essential data of the system for quantification. Program item 4 which involves a degree of judgment is of equal importance

in developing reliable procedures.

4. The computer program has access to a very complete library of data on thermal

neutron generated activities. Relevant

data on both sides of the energy of the

peak of interest over any desired energy

span is easily evoked and printed out. Along with the gamma energies there is

printed out: nuclides, half lives, abundances, cross sections, accompanying

gammas.' This information allows, in most

instances, decision as to identity , as well as quantitation ; in some instances

additional information from decay is re- quired. Energy and decay data generally

are adequate for positive identification

as well as quantitation.

5. Decay information of a given peak or

set of peaks in a sequence of counts is

always desirable in developing procedures

for samples of a newly given set. The use

of the tape for recording a set of samples'

changing spectra with time by repetitive

counting in the mechanical sample changer

gives a set of data that can easily be

used for this purpose. Thus, suppose 18

samples are counted ten times in a 48-hour

period. Then the tape data in the computer are queried for a given peak (region

of interest per program item 1) in repetitive spectra for a given sample or samples

and the results plotted using a simple

least squares statistical evaluation to obtain the decay constant for each nuclide

peak of interest.

RESULTS

Figure 3 shows typical information

obtained by gas chromatographic examination of tar balls. Figure 4 shows some typical information which may be obtained

by means of neutron activation of tar

balls. Table 1 (Guinn 1970) shows that a variety of oils may be readily monitored

by neutron activation. All of the data

taken in this demonstration of trace elements in tar balls are given in Table 2. Comparison to the data in Table 1 suggests

that significant trace element content in

tar balls should be considered for ecological impact evaluations for both oils and

tar ball residues (Feldman 1973a).

PI)

Figure 3. Typical information obtained by gas chromatographic

examination of tar balls.

239
••%f

512

56 Mn

047

SAMPLE 323

TB 362-1 15% OT UT6602 044

10 K Full Seal*

No"

1368

CI""

1642

No"

1731

Mn

1811

56

Comma Entrgy

Figure 4. Typical information obtained by neutron activation

of tar balls.

TABLE 1

Instrumental Neutron Activation Analysis Results

on 16 Different Marine Fuel Oils

ppm Concentration Found Number V Mn Na Co

1 17.5 <0.30 35 0.92

2 175 0.043 7.9 0.39

3 220 0.020 1.69 0.62

4 470 0.077 44 0.41

5 77.6 <0.37 108 1.84

6 170 0.011 2.12 <0.07

7 3.8 0.002 0.36 0.08 8 865 <0.19 38 0.13

9 91 <0.39 25 0.40

10 250 <0.24 19 0.40 n 126 <0.23 7 0.23

12 284 0.08 12.4 0.25

13 292 <0.28 85 0.35

14 208 0.07 6.3 0.21

15 152 0.24 32 0.57

16 57.5 0.113 13.3 <0.08 CGu1nn,1970]

240
TABLE 2

Tar Ball Analytical Results

ppm Dry Weight Found

ID# Mn Na Zn

362-1 15.5 + .32 362-3 3.95 ± .30 362-4 44.4 ± .39 364- 3 61.3 ± .62 365- 8 32.1 ± .37 365-14 5.24 + .25 367- 2 12.2 ± .76 368- 3 15.1 + .77

SUMMARY

Neutron activation procedures applied

to a set o£ tar ball samples have readilydemonstrated and quantitated some trace

elements in tar balls. These preliminary

I results show that such a methodology can

add to the information obtained in monitoring tar balls and their presence in

various seas by further evaluating their

composition. It is believed this procedure can be very useful in evaluating

the ecological impact of surface films of

j oils and other materials present in the

i surface slick on marine waters (Feldman

] 1973a).

ACKNOWLEDGEMENTS

We are indebted to James Butler

(Harvard, Department of Applied Physics)

and Byron Morris (Bermuda Experimental

Station) for permission to examine some

of their speciments.

All of the INAA work described was carried out at the Oregon State University Radiation Center. We are indebted

to Dr. Chih Wang, Director, for permission to utilize these facilities.

Disclaimer: Mention of trade names or commercial products does not constitute

endorsement or recommendation for use. REFERENCES

i

I Blumer, Max, P. C. Blokker, E. G. Cowell,

D. F. Duckworth. 1972. "Petroleum",

Chapter 2 in A Guide to Marine Pollution . E. D. Goldberg, ed. Gordon and Breach

Science Publisher. New York City, 1972.

Butler, James N. 1973. National Academy

of Sciences Workshop, Imputs, Fates, and

Effects of Petroleum in the Marine

Environmenti May 21-25, 1973, Airlie,

I Virginia. Section on Fates,

! J. N. Butler, ed.

Farrington, J. W. , C. S. Giam, G. R. Harvey, P. L. Parker, J. Teal. 1972.

Ton J. 13.9 ± .09 / on

( 80. + CO \ 62.) 12.7 ± .09 ( 94. + 79.) 2.67 ± .02 3.83 ± .03 ( 65. + 54.) 4.82 ± .05 10.4 ± .10 5.94 ± .06 (166. ± 107.) 8.64 ± .08 (176. + 92.)

"Analytical Techniques for Selected

Organic Components," in Marine Pollution

Monitoring; Strategies for a Nationar

Program . E. D. Goldberg, ed. NOAA, U.S.

Dept. of Commerce, Washington, D.C. 1972.

Filby, R. H. and K. R. Shah. 1971. "Mode

of Occurrence of Trace Elements in Petroleum and Relationship to Oil Spill Identification Methods," in Proceedings.

American Nuclear Society Meeting:

fJuclear Methods in Environmental

kesearch" Aug. 21-23, 1971, University

of Missouri, Eds: J. R. Vogt, T. F. Parkinson, R. L. Carter.

Feldman, Milton H. 1973a. Petroleum

Weathering: Some Pathways, Fates, and

Disposition on Marine Waters. Environmental Protection Agency. 660-3-73-013,

August 19 73. Feldman, Milton H. , David E. Cawlfield,

Kenneth V. Byram. 1973b. Environmental

Monitoring; Radioactivation Analysis of

Sludge and Sediment Constituents (in

preparation)

.

Garrett, W. P. 1967. The Organic Chemical

Composition of the Ocean Surface. Deep

Sea Research 14, 221, 1967.

Guinn, V. and S. C. Bellanca. 1970.

Neutron Activation Analysis Identification of the Source of Oil Pollution of

Waterways. National Bureau of Standards

Special Publication 312 Volume 1, p. 185.

Washington, D.C. 1970.

Levy Eric. 1973. The Quantitative

Determination of Trace Concentrations of

Petroleum - Derived Pollutants in the

Ocean. National Academy of Sciences Ocean

Affairs Board, Workshop on Inputs, Fates,

and Effects of Petroleum in the Marine

Environment. May 21-23, 1973. Airlie,

Virginia. Section on Analysis, ed.

F. T. Weiss.

Koons, C. B. 1973. Private Communication.

This fact is also pointed up in the Fates

Section of the NAS Report: See Butler (1973

241
V
NBS Spec. Fubl. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Sy^posi-m and Workshop held at NBS, Galthersburg, Maryland, May 13-17 1974 (Issued December 1974).

DISTRIBUTION OF TAP BALLS AND NEUSTON SAMPLING

IN THE GULF STREAM SYSTEM

K. Sherman, J.B. Colton, R.L. Dryfoos

K.D. Knapp, B.S. Klnnear

National Marine Fisheries Service

Narragansett, Rhode Island U2882

Significant amounts or tar balls were ob- served off the east coast of the United States during surveys of larvae fishes and their environment in summer 1972 and winter 1973. The principal objective of the investigation vias to locate spawning areas of important recre- ation and commercial tishes (tunas, billtlshes, bluefish, mackerels, and others) and determine the influence of the Gulf Stream

system on their distribution and abundance. The area of operations extended from Cape Cod

to the Caribbean.

100» 90» 80" 70'> 60° 50" 40"

Figure 1. Location of neuston collections made

during MARMAP surveys.

Vessels or the National Marine Fisheries Service

(NMFS), State of South Carolina, University of Rhode Island, and the Polish Sea Fisheries Laboratory participated in the survey. Operations were conducted as part of the MARMAP program of NMFS, which is designed to systematically assess, monitor, and predict seasonal and annual changes

in demersal and pelagic fish stocks.

A series of standard collections were made for fish eggs and larvae (ichthyoplankton) in the water column and at the surface. The findings

described herein, are limited to the results of

the surface tows for larval fish and other neuston organisms. All neuston tows were made

at the air-water interface with a one by two meter neuston net at a speed of 5 knots for 10 minutes, and filtered about 3,0a6m2 per tow.

The net bridles were adjusted to sample in the upper half meter of water. The net used was constructed of 0.94mm mesh with a minimum ratio

of mouth opening to net filtration of 1:11.

Tar balls i were observed clogging and meshes and were considered initially as a nuisance factor. However, their persistent occurrence in the sam- ples was noted and with few exceptions they were

retained for an analysis of their distribution.

In the laboratory all the tar was removed and

and dried weights determined in grams for each

of the samples.

The amounts of tar retrieved from the samples is considered minimal. In the initial samplings

some tar was discarded at sea. In heavy seas the neuston net did not effectively sample tar balls

that were mixed in the upper several meters by

wind-induced turbidity. And at the towing speed

ot 5 knots significant amounts of tar are extruded through the meshes

TAR BALLS DISTRIBUTION

Initial results from the summer survey indicate

that tar contamination of surface waters in the Northwest Atlantic is not an isolated phenomenon,

but is widespread. Larval bluefish, flounder,

tuna, blue marlin, and other important resource

species were collected in neuston nets contaminated with tar.

Average concentration of tar balls were compared

among six geographic areas; heaviest average con- tamination in summer, 3.9mg/m'^, was in the region

north and east of the Bahamas and Antilles. Av- erage values for the other areas did not exceed

O.omg/m^, Our examination of the neuston samples

collected in winter (January-March 1973) from

Cape Cod to the region north of the Antilles

showed that tar balls were again most heavily

concentrated north of the Antilles; average sta- tion value was A.8mg/m^. Average values for the other areas were comparatively low, 1.3mg/m . A summary of the weights ot tar balls by station

on both the summer and winter surveys is given

in Table 1.

Although sampling variation has not been subjected to rigorous analyses, we noted that low tar amounts were found from offshore Virginia to Cape

Cod in winter this may have been caused by a samp- ling bias. Unusually rough seas were encountered

offshore in winter and the sampling efficiency of

the neuston net is reduced when tar balls are mixed in the upper few meters in turbulent seas.

The area north and east of the Antilles sampled

on both surveys represents the western boundary

region of the Sargasso Sea. It is not surprising

to find the heavy concentrations in this region,

which is a large eddy that concentrates floating

objects including Sargassum Weed. Flotsam is accumulated from the rapidly moving waters of

the current about the periphery of the eddy, the Gulf Stream on the west and north, Canary Current

on the east, and North Equatorial and Antilles

currents to the south.

243
Table 1

PERCENT OCCURRENCE, AND AVERAGE CONCENTRATIONS

(mg/m2) OF TAR BY AREAS IN SUMMER 1972 CJULY- AUGUST 1972) AND WINTER 1973 (JANUARY-MARCH

1973) DURING MARMAP SURVEY OPERATIONS

SURVEY REGION NO. OF PERCENT CONCENTRATION NEUSTON W/TAR mg/m^

TOWS

Va-Cape Cod 29 31 O.lB

(coastal)

Va-Cape Cod 29 38 1.04

(coastal)

Va-Cape Cod 52 83 0.77

(offshore)

Va-Cape Cod 51 59' 0.05

(offshore)

Petroleum residues (tar clumps) have been found throughout the Atlantic. Morris and Butler [3] estimate the standing stock at 86,000 metric tons with concentrations in the Sargasso Sea 3.6 times greater than the average wet weight of daytime

zooplankton (9.4 versus 2.6gm/m2). Tar clumps

constituted about 20 percent of the weight of surface samples (neuston) of zooplankton collected by them in the western Atlantic on a transect taken south of the Grand Bank between

42' N and 3&»N.

The effect of petroleum residues on the production cycle in the sea is not clear; laboratory

Investigations and in-situ investigations on phytoplankton contamination by oils are presently

underway Gordon and Prouse [^J* The effects ot petroleum residues on the ichthyoplankton is not understood; under laboratory conditions oil com- pounds extracted from oil tilms have been shown

to be toxic to fish eggs and larvae Krunhold [5] MironOv [6].

N.C. -Florida 32 78 (Gulf Stream)

N.C. -Florida 48 yO

(Gulf Stream)

N. Antilles & Bahamas 39 87

N. Antilles & Bahamas 't7 96

0.23

1.22

3.9

4.8

The effects of zooplankton viability is also not clear Nelson-Smith

REFERENCES

[1] Butler, J.N., J.C. Harris, and K. Fine,

"Preliminary Gas Chromatographic Analysis

of Pelagic Tar samples for MARMAP Survey,"

unpublished NMFS contract report, Sept. 1973. Harvard University, Cambridge, Massachusetts,

02138.

(S-Summer & W-Winter)

COMPOSITION OF TAR BALLS

Pelagic tar from zO samples were sent to Dr. James Butler at Harvard University, Cambridge, Massachusetts, for analysis, ihe samples were analyzed

by low resolution gas chromatography to obtain

semi-quantitative profiles of normal paraffins

in the range from C12 to C35, and a quantitative

indication of the relative amount of other

compounds having a volatility in that same range. Two-thirds of the chromatograms showed bimodal

paraffin distribution, in the IJ20 to C35 range characteristic of crude oil sludges. This is evidence that these tar balls come from tanker wastes dumped at sea. one sample was almost

all paraffins. The samples mostly were weathered residues of waxy parafflnic crude oils, and similar with respect to the parameters measured

for numerous samples collected in the Sargasso

Sea near Bermuda [1].

Jeffrey et al [2] , recently completed an analysis

of tar balls collected with neuston nets in the Gulf of Mexico and Caribbean Sea. Extraction of pelagic tar aggregates revealed that 3/ percent

ot tar mass was debris. Including rust, wheat

grains, clay, silt, and other constituents.

Average concentration os debris-free tar in the Gulf and Caribbean were 0.88 and o.74 dry mg/m^

respectively. Suspected major sources of the tars are tanker tlushings on the shelt and waste dumping over the continental slope.

[2] Jeffrey, L.M., W.E. Pequegnat, E.A. Kennedy,

A. Vos and B.M. James, "Pelagic Tar in the Gulf of Mexico and Caribbean," draft manuscript, Sept. 1973. Department of Oceanography, Texas A&M University, College Station, Texas 77843.

[3] Morris, B.F., and J.N. Butler, "Petroleum

Residues in the Sargasso Sea on Bermuda

Beaches. Proceedings of Joint Conference

on Prevention & Control of Oil Spills,"

March 1973. Washington, D.C. 20002.

[4] Gordon, U.C, Jr., and N.J. Prouse, "The Effects of some Crude and Refined Oils on Marine Phytoplankton Photosynthesis." ICES: CM 1972/e:33.

[5] Krunhold, W.W., "The Influence of Crude Oils on tish Fry. FAO Tech. Conf . Mar. Pollution and its Effects on Living Resources and Fishing," December 1970. rIR:MP/70/E-64,

Nov. 1970.

[6] Mironov, O.G., "Hydrocarbon Pollution of the Sea and its influence on Marine Organisms,"

Helgolander Wlss. Meeresunters 17, 1969.

[7] Nelson-Smith, A. "The Problem of Oil Pollution of the Sea. Advances in Marine Biology,"

8;215-306.

244
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Gaithersburg, Maryland, Hay 13-17, 1974 (Issued December 1974).

ESTIMATION OF THE MODERN OIL POLLUTION

OF THE NORTH ATLANTIC WATERS

A. I. Simonov, S. G. Oradovski,

and

A. A. Justchak

Oceanographic Institute

Moscow, U.S.S.R.

The investigations made during the

1972-73 expeditions by vessels of the

USSR Hydrometeorological Service in the

North Atlantic permitted estimation of

the spatial and vertical distribution of

oil products in waters of this, the most

important region of the World ocean.

The dominant role of fluid dynamics

in the distribution of these pollutants

is determined. The minimum concentrations of oil products are found in midstream areas of the Gulf Stream and the

North Atlantic current. The maximum

concentrations are found in the peripheral regions of these circulation

systems and also inside of the gyres of

different types and origin. These characteristics of spatial distributions of

oil pollution are presumed to be caused

by processes of turbulent diffusion.

The velocities of the main flows are not

uniform. Observations showed that where

sharp gradients are formed, intensive

turbulent transfer from midstream to the

periphery is caused by the cross current

component. As a result, the main flow

is free of oil products which are con- centrated on its periphery.

The vertical distribution of oil

products is characterized by greater

variety, because some fractions of these

pollutants have different physical characteristics, particularly, different

specific gravities. The light fraction

oil film probably behaves like detergents

when first thrown into the sea. The

vertical distribution of the heavy fractions is similar to that of mercury distribution. Finally, the emulsified and

dissolved fractions are distributed

regularly through the vertical water

column; these distributions follow regular patterns that are dependent on specific hydrodynamic factors.

Regions adjacent to the North

American and the Western European coasts

are the North Atlantic areas most

polluted by oil and oil products.

245

TOPICAL SESSION VI. Biological Assessment

247
Cf
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

VALUE OF OIL POLLUTION MONITORING

IN MARINE ORC^ISMS

Gllles La Roche

The Consortium on Water Research

6600 Cote des Nelges Road - Suite 211 Montreal, P.Q. H3S 2A9, Canada

The principal force motivating an international program for petroleum monitoring is un- doubtedly western world opinion which recognizes

the great environmental dangers of excessive vo- luntary or accidental discharges. The most fea- red environmental effects are those impairing

the ocean environment, while it is understood

that, in this instance, one is referring to the biological productivity of the oceans. We are therefore worried that petroleum products , or rather excessive discharges of petroleum products

will impair the biological productivity of oceans, coastal areas and estuaries. To satisfy this le- gitimate concern, two fundamental needs must be

fulfilled before monitoring can be successful. First of all, there must be monitoring of rele- vant or representative tainting products , which

implies an identification of harmful fractions

secondly, a range of biologically or esthetically tolerable concentrations of tainting products

must be established.

At present, I submit that we only have res- tricted knowledge of either of these conditions.

In other words, we are now planning to measure hydrocarbons in water, without knowing precisely

which are the most harmful and in what concentrations these products can be tolerated. We may

thus be responding primarily to panic. We may

also be doing something because action is better

than inaction. This, in my opinion, could represent buoy work which could unfortunately represent excessive expenditures once we know what to measure, how much of it can be safely tolerated

by the environment. The two more positive features of monitoring can be that it will encourage

the kind of international cooperation: and coordination essential for the reporting system and it will keep world opinion focused on the problem as it gets more dramatic. In that same vein, there

are additional dangers in setting up such a monitoring system without adequate inputs from biologists. For instance:

1- public knowledge that petroleum monitoring is underway may give a false sense of security

to those who assume that, because something is being continuously measured, the danger has lessened;

2- the monitoring methods themselves may be obsolete before the tainting agents and their critical concentrations are established;

3- the deterioration of productive coastal or es- tuarine areas may proceed at a faster rate

than the identification of harmful products

are made.

At the moment, to give warning of oil slicks

entering coastal waters or approaching fishing

areas would be next to useless since, in all pro- bability, the choice of contingencies could be un- acceptable. For instance, the spilled oil might

be: 1- dispersed, which would render it more toxic

to most organisms, with the possible exception of those capable of fleeing affected areas, or, 2- attempts could be made to collect it, using current

techniques; this would hardly be effective and,

at best, could assist In saving some real estate

or personal property values

My proposition is that, now or in the immediate future, as the refinements of world monitoring

proceed, we also must invest reasonable efforts to establish the water quality criteria for the survival of desirable ecosystems, with respect to fossil fuel hydrocarbons , In other words , what

concentrations of these hydrocarbons can ecosystems safely tolerate? This still remains to be

established, and will remain so until we devote

enough efforts in this direction. At present. Annexe V and its appendices represent logical structures for reporting, but again, these structures are resting on shifting sand, if I may use

the metaphor. It is not until we know the quality

and quantity of material to be detected that we

can realistically report dangers to the environment.

Presently, one of the favored demonstrations

of toxicity to various marine species is a test, referred to as the TL50 or LD50, whereby animals

are submitted to products for a period of 96 hrs

under artificial conditions. On one hand, it should be stressed that the 96-hr. LD50 is not a legitimate evaluation of product toxicity since it deals primarily on a scale of life or death over

an arbitrary period of 96 hours of exposure. On

the other hand, the test can be useful in establishing concentrations of test products to be used

in long-term experimental exposures aimed at identifying subtle but significant biological impairments . This latter type of experimental work

would mean that concerted interdisciplinary work

would evaluate the chronic impact of oils on key

species. In these studies, continual monitoring

of pollutants, with time, is important. Chronic

exposures would thus be coupled to systematic de- tection schemes for the evaluation of anomalous

developments in larval, intermediary or adult

forms. The approach would, of course, represent

sizeable expenditures. However, it is doubtful

that any real progress will be made unless significant biological anomalies can be related to pollutants in realistic concentrations, over realistic periods of time and under realistic conditions.

Recently, the Marine Technology Society has

sponsored a workshop of scientists from several

disciplines and belonging to three important sectors of society: the university community, the government and industry. This interdisciplinary

group, including behaviorists , engineers, chemists,

biochemists, pathologists, biologists, etc., will

develop experimental approaches whereby various

coastal ecosystems will be studied to evaluate

the extent and significance of biological damage

249
caused by pollutants, alone or in realistic combinations. The evaluation stuHips would be made in

the classical manner, that is, in all instances,

controls would be examined at regular intervals and compared to exposed organisms

.

Various aspects of probable changes would

then be made. In a first tense, gross evaluations would be made on pigmentary responses, ec- toparasite distributions and diversities, oxygen

consumption, swimming performances, gross behavioral anomalies, etc. In a second step, early

or obvious changes would be pursued by more pro- bing tests which would include blood counts, biophysical properties and enzymology, followed by

histopathology , histochemistry and cytopathology

.

Studies would attempt to Identify morphological,

functional or developmental anomalies directly

related to specific pollutant exposures , under

realistic and adequately monitored conditions.

Probable synergistic and antagonistic effects of pollutants would receive attention in experimental programs as similar to normal environmental

conditions as can be effectively attained. In associated studies, evaluation of contamination

and decontamination rates of various tissues

would be made. Estimates of metabolic transformations and increased contamination of predators

would receive attention. This would, of course, provide public health impact of contaminated or- ganisms .

In the development of experimental procedures, the following tasks will be assumed by

the participating scientists. First, a select

group of test organisms will be developed; in general, the species chosen will have been exten- sively studied by scientists in the past. Secondly, there will be a need to establish the envi- ronmental parameter ranges these species can be

expected to normally withstand; thirdly, there will be a need to establish the normal range of each biological parameter of test organisms and their significance as index of well-being; fourthly, it will be necessary to establish biological parameters which provide clear indications of particular anomalies ; great advantage would be

derived if these indices or symptoms can be re- lated directly to particular types of pollutants

or combinations of pollutants. Finally, it will

be necessary to compare the response of organisms

to the environmental parameters in the presence

of pollution or pathogens , or combinations of either naturally occurring diseases and abnormal

concentrations of pollutants. Relationships

could then be established between the biological

and environmental changes of natural populations

as defined experimentally. From this, it is ex- pected that realistic tolerable levels of pollution in the environment would be Identified.

These levels would then be equivalent to water

quality criteria to the various species studied

and, as originally planned, these criteria, ha- ving been modulated by social and political re- quirements, would assist in the elaboration of realistic standards.

To pursue this type of experimental work,

which must be verified under near-natural conditions , it is anticipated that extensive oceanographic and atmospheric information will be

needed in order to simulate and understand the physical and biological interplays of various

types of environmental conditions and petroleum

products. Experimental work on biological systems

could advantageously benefit from or serve the pilot project on marine pollution monitoring; for instance: field observations can be essential to establish realistic experimental conditions. Also,

the siting or measures of definite oil concentrations resulting from spills could be related with

verified experimental findings and reveal, with

some accuracy, the resulting damage to particular

ecosystems. The studies on- pathological developments of various species would serve this same monitoring program in establishing that various

concentrations of petroleum, entering certain

areas, are likely to cause a specific damage, in that some or most species will be seriously impaired. Appropriate measures could be taken, such as those involving the replacement of key species after a period of time is allowed for the depuration

of the affected areas. It would appear that the development of biologically compatible cleaning-up

operations will have to be tested through the com- bined efforts of chemical-monitoring and biological testing programs. Much can be learned from

spills in the environment, such as that of the Torrey Canyon and the Falmouth incidents . However, appropriate experimental work, integrated

with field observations , would ensure that field measurements are relevant and that these will

help in defining criteria rather than merely predict catastrophies

.

For this reason, I would strongly suggest

that intensive coordinated efforts be made by the world scientific community to establish the precise nature of products which are biologically

damaging and how much of these can be tolerated by a viable environment. I would also recommend

that Annexe V advocates close exchanges of information between monitoring and biological scientists. This could ensure that chemical monitoring

will reveal the conditions necessary for the esta- blishment and eventual enforcement of biological

criteria and standards.

Key Words : marine organisms , biological productivity, water quality criteria, TL50 or LD50, long- term exposures, interdisciplinary work, test organisms .

250
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

EFFECTS OF OILS ON BALTIC LITTORAL

COMMUNITY, AS STUDIED IN AN OUTDOOR MODEL

TEST SYSTEM

M. Notini and X. Hagstron

Swedish Water and Air Pollution

Research Laboratory

IVL Baltic Laboratory Studsvik

Fack S-61101 Nyhopingil

Sweden

Introduction

A proper evaluation of the nature and

extent of biological effects caused by

oil spills at sea is a necessary but

difficult task. For example as pointed

out by Grassle [1] there is a great un- certainty as to where in the ecosystem

and by which means studies with this

aim should be performed.

In the Baltic Sea ecosystem the littoral zone is of major importance. The

archipelago of this inland sea comprises more than 20,000 km2 representing

about 6 % of the total area. This highly diversified zone is responsible for

much of the primary production of the

Baltic and constitutes food chains with

endpoints in about 50 species of fish

and 40 species of birds [2].

The Brown alga belt, consisting mainly

of Fucus vesiculosus harbors about 70 I of all Baltic macrofaunal species [3,4]

Therefore it was felt pertinent to fo- cus on the dynamics of the littoral

zone when we tried to develop a test

system for evaluation of effects of oil

pollution in the Baltic Sea. The aim of

our study was to develop a method for

this type of evaluation that is convenient to use under field conditions during and after a real oil spill. The method was tested in outdoor model systems, simulating realistic littoral con- ditions, where the different environmental parameters could be well controlled.

Test system

Plastic swimming pools made by Cranpool were used for the model systems. The pools

(water surface, 7.3 m^ , volume 4.8 m^) were equipped with a flowthrough system

providing '\^2 . 5 1/min and designed to prevent oil from leaving the system as illustrated in figure 1. The main components

of the Baltic littoral ecosystem were f then introduced into the pool to form a

balanced model system. Fucus vesiculosus occupied 1/3 of the sand covered bottom.

Twelve roughly equally sized plants

(100-200 gr wet weight) attached to small

stones were distributed amongst the rest

of the Fucus in each basin, comprising

10 I of the total weight of Fucus. Each

of these plants was placed in the middle

of a folded polyethylene bag which was covered with sand. The floral and faunal

elements were all collected in the neighborhood of our laboratory (90km south of

Stockholm) . The systems were set up in

late July and the beginning of August

1973 and allowed to stabilize prior to any experimental stress. The tests were performed during the period September, 5

- October, 26 1973. Simulation of an oilspill was accomplished by adding a single

dose, 4.8 liters (1000 ppm) of oil to the

test system at zero time. This should, if

evenly distributed, give an oil layer of

'V' 0.7 mm thickness. Three different oils were used in the test: Light fuel oil

(diesel type) , Medium fuel oil and Nigerian crude oil. The sampling procedure

is illustrated in figure 1. At intervals two samples of Fucus including the

faunal elements were taken from each basin. Samples were taken immediately before the addition of oil and 3, 7, 15,

33 and 54 days after zero time. In order

to minimize the loss of animals during

and after sampling the whole plant was immediately brought to the laboratory

for examination. The wet weight of the

Fucus was determined and only living

animals were sorted and counted. The

material was divided into 15 systematically defined groups.

LrrroeAL MoOEi- ECoSySTEM

MAIH F6ATiJR.ES OP E*PEeiMEKT7M. SE-TtlP

Figure 1.

Method of evaluation

As exemplified in table 1 the resulting

lists of systematic groups and numbers

of individuals give a somewhat confusing

picture. The results from the test with

light fuel oil showed more obvious effects, although much less dramatic than

the visual appearance of the massive

kill observed in the test. The tabulated

251
Light

fuel oil

I

I5sMedium

fuel oil

Table 1

2 S- S'S <3-5.

42 15 260 444 383

41 31 247 242 234

27 S 152 123 199 38 8 124 195 175

24 8 207 233 408

S3 5 136 169 169

274 133 161 306 175

107 63 258 687 139

6 9 573 265 159

5 55 343 382 165

12 30 573 184 42

0 9 444 865 170

56 IS 152 102 213

6 16 75 124 182

4 21 312 216 138

0 0 391 97 131

0 0 67 10 95

0 0 70 3 4

d

^ d i&

z . as s sr 2 >

1- o

o H_ H O <'S

1226 13 10

871 14 12

540 9 7 868 11 9

1132 13 12

774 15 12

1406 12 10

2189 9 8

1748 9 8

2246 10 8

961 9 7

2068 7 6

689 11 10

419 8 7

752 12 9

712 9 9

229 6 6

81 6 4

in which a is the number of species in the

first sample, b is the number of species

in the second and c is the number of species occurring in both.

The relative abundance of species is con- sidered in the percentage similarity of

community PS .

PS^=100-0 . 5E(a ' -b ' )=Z min(a', b')

in which a' and b' are for each species

the percentages of the total number of

animals in samples A and B respectively.

Both indices take values between 0 and 100,

which represent the lowest and highest

affinity, respectively, between two samples . Results and discussion

In figure 2 the samples from the two control basins A and B are compared in so called Trellis diagrams. The diagrams

below in figure 2 show the high degree of

similarity between samples taken at different times within each control basin. To check the possibility that there might be

differences in community structure between

basins, we compared the two replicate control systems. As illustrated below they

Average number of indVlOO g Fucus wet weight Some of the most abundant

systematic groups in samples taken during the experimental time.

results of the treatment with the less

toxic medium fuel oil are much less

clear. Obviously we had to find a method

of evaluation giving a sufficiently detailed description of changes in community structure, e.g. by means of some biological indices. In studies on effects

of water pollution, diversity indices

applied on benthic faunal communities

have successfully been used [5,6,7],

But this type of index requires material

determined at the species level, which

in this case, was considered too time

consuming. For our purposes the use of

affinity indices calculated from higher

systematic groups was decided to be more

convenient. If these selected systematic

groups are defined after the actual

needs it is meaningful to use such an index to assessthe degree of similarity

between samples. Two types of affinity

indices were used, the coefficient of

community and the percentage similarity

of community as reviewed by Johnson and

Br inkhurst [8]

The coefficient of community, CC , measures

the percentage of species shared by two samples as

Control B

Stability of test system. Similarity between samples taken at

six occasions from two control basins A and B (above), and between the two basins (below). CC= COEFFICIENT OF COMMUNITY

PSc = PERCENTAGE SIMILARITY OF COMMUNITY

51-65% 11 66-100% CC

b - c 100 Figure 2.

252
seem to be very similar. This is also the case when the first sample from the test

basins is compared to the samples from the

control as seen in the first row in each

Trellis diagram in figure 3.

In the test with light fuel oil (fig. 3)

the values of the CC index were soon strongly affected. The PS index, however,

reacted rather slowly. Thi light fuel oil

with its high amount of low boiling aro- Jo

mates and consequently high acute toxicity

soon gave a complete extinction of many

systematic groups of animals, and this will

affect the CC index. But since the exposure to the oil reduced the number of individuals rather unspecif ically and probably not caused great changes in relative

composition the ps^. index is little affected during most of the test period. This

unspecified affect gives in this case specific damage in the ecosystem since a lot of the less abundant groups can be

completely eradicated and thus giving rise

to an unbalanced ecosystem.

The Trellis diagrams from the basin with

medium fuel oil (fig. 3 below) give the

opposite impression. The reduction in

PS(- index values is more pronounced than

that of the CC index. It should be observed that this reduction is noted immediately. As the CC index seems rather

unaffected we conclude that some abundant species must have been reduced but

not extinguished during the test. This

could be explained if we assume that

some chemical or physical property of

the oil changes during the test period.

For example a reduced stickiness of the

oil surface or lower dissolution due to the formation of a water in oil emulsion,

i Since the Nigerian crude oil gave

an intermediary picture compared to the

tests on light fuel and medium fuel oil it

has been excluded in this presentation.

'The crustacean group Gammarus spp can be

used to illustrate the different effects of

the tested oils. Most crustaceans have a body surface with a cuticle which is co- vered with a hydrophobic wax layer [9] . In Gammarids this is very pronounced and

these animals are therefore very sensitive

to lipophilic substances. As seen in figure 4 all three oils cause a rapid reduction in numbers of individuals in the

samples. But while in the light fuel and

Nigerian crude oil the Gammarids are com- pletely extinguished after one week they

are present in the medium fuel oil

throughout the test period. In the control

the abundance of Gammarus spp is relativele constant with time.

PS,

Control

mm

time

1 5 2 a

,In the experiments the animals were

!pri: -ented from leaving the basins

an :hus the results obtained could be

far too drastic compared to those obtainable under field conditions. We therefore

checked this on a number of samples of

the Fucus attached fauna gathered in the

field. In October 1970 the small bay of

Gastviken in the Stockholm archipelago was

PS

Effects of oils on the littoral community in the model test system Changes in faunal affinity as comapred to the control basin CC= COEFFICIENT OF COMMUNITY

PSc = PERCENTAGE SIMILARITY OF COMMUNITY

100

MEDIUM FUEL OIL

LIGHT FUEL OIL

r^fi"" "A""" ^

0 10 20 30 AO 50

CONTROL

NIGERIAN CRUDE

100

75

50

25 0

75

-50

-25

0 10 20 30 AO 51 TIME (DAYS)

51-65% I 66-100 % REDUCTION OF GAMMARUS SPP. IN FUCUS SAMPLES

FOLLOWING OIL SPILLS.

Figure 3. Figure 4.

253
polluted by a massive oil spill. Approximately 400 tons o£ medium and heavy fuel

oil drifted into the bay under a strong

wind. The Swedish coastguard managed to enclose the oilslick with bars across the

Bay. Most of the oil was then collected

mechanically during the winter, and in

the middle of May 1971 the operations were finished. During this year Fucus

samples were taken on four occasions and

on one occasion the following year as part of a recovery study in the area.

In 1971 single samples were taken in

June, July and November at two stations

in the bay (A and B) . In a nearby un- polluted l3ay (R) one sample was taken

in July 1971, and was used as a refe- rence point (fig. 5). In July 1972 three

samples were taken at both station A and

B. The method used was similar to the one described for the test system. In this case the algae were enclosed in the plastic bag from above before the plant was

cut off the rock at the ritsom region.

The samples taken gave us the opportunity to compare the samples from the

polluted bay in the first year (1971)

to references in time and space, namely

the 1972 samples from the stations in

the bay and the 1971 R sample. As seen

in figure 5 the two stations A and B react in a similar way. When comparing

the June 1972 samples to the samples

taken in June, July, August and November 1971 a very low similarity to the

first months can be observed. In August,

however, the higher affinity seen es- pecially in the PS^- index must be attributed to a recovery by migration of

dominant species into the bay.

Effect on littoral community at Gastviken bay

following a medium fuel oil spill CC = COEFFICIENT OF COMMUNITY

PSq = PERCENTAGE SIMILARITY OF COMMUNITY

Scale 65% I 66-100 %

Figure 5.

If the 1971 samples from station A and

B in Gastviken are compared to a sample

from the reference station R in July the same year, the pattern is identical.

Note that in both these comparisons the

PS|- indices are the most affected which

might have been expected since this also was the case in the test system with me- dium fuel oil.

As seen in figure 5 above it seems that

the sampling method is rather accurate

since the affinity between the three subsamples in June 1972 is high.

In conclusion we have found the above described method of using changes in the

structure of Fucus communities both rapid

and sensitive in measuring effects due to oil pollution in the Baltic littoral fauna

Acknowledgement

:

This work was supported by grants from:

The Swedish Coastguard; the National

Environment Protection Board; and the

Swedish Petroleum Institute.

References

:

[1] Grassle, I.F. Background paper for a workshop May 21-25, Airline, Virginia

Vol. 1, pp 323-346 1973.

[2] Jansson, A-M. Contr. Askolab . Univ.

of Stockholm, Sweden _5 129 pp 1974.

[3] Haage, P. Zoologisk revy 31 1-2 pp pp 21-22 (1969).

[4] Haage, P. and Jansson, B-0, Ophelia 8 Dec pp 187-195 (1970)

[S] Mathis, B.J. and Dorris, T.C. The

American Midland Naturalist 80 (2)

pp 428-439 1968

[6] Rosenberg, R. Qlkos 23 pp 92-108 (1972)

[7] Copeland, B.J. and Bechtel, T.J. Water Air and Soil Pollution 1 pp 89-

lOS (1971)

[8] Johnson, M.G. and Brinkhurst, R.O.

J. Fi sh. Res. Bd Can, 28 (11)

pp 1683-1697

[9] Richards, A.G. Minneapolis Univ.

Minnesota Press 4411 pp 1951.

Key v/ords: Affinity indices; Baltic

littoral community; field study; model

test system; oil spill; toxicity.

254
NBS Spec. Publ. 409, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

HYDROCARBON CONTENT AND CHLOROPHYLL

CORRELATION IN THE WATERS BETWEEN NOVA

SCOTIA AND THE GULF STREAM

A. Zsolnay

Bermuda Biological Station,

St. George's West, Bermuda.

Several laboratory experiments have

shown that phytoplankton produce hydrocarbon material Ll 5 2 , 3 , . Therefore one would expect that a certain

amount of the hydrocarbon material found

in the marine environment is from this source and that a correlation between

hydrocarbon content and chlorophyll

should be present. The author has found

this to be true in the euphotic zone of

the upwelling waters off Northwest Africa

[5]. One drawback to the data that was accumulated there was the fact that the

method used was not capable of providing

the absolute values for the hydrocarbon

concentrations and the values given were purely relative ones. This is unimportant in a correlation study dealing with

one particular region but can be a ser- ious handicap in comparing one region to another. In this study it was possible

to use an improved method, which enabled

the absolute concentrations to be

determined in a body of water with

considerably different hydrographic

properties from the upwelling water.

The samples were taken on the CSS

DAWSON in the euphotic zone at 1, 10,

and 25 m at 8 stations during a cruise

toward the end of July 1973. The

stations were on a line that went almost

due south from Nova Scotia to the Gulf

Stream. The method used is described

in greater detail in another part of

this volume and in the literatureC63

.

It consisted of extracting 1 liter of the

sea water sample with a non-polar solvent

at sea and then concentrating the

extract in the laboratory. The hydrocarbons were separated from non-hydrocarbon material by means of high

performance liquid chromatography and were then detected by a flow calorimeter.

Duplicate samples were run whenever

possible and blank values subtracted.

Each value had a standard deviation of

+ 3.1 yg/l.

The chlorophyll content was determined

at the AOL laboratories of the Bedford

Institute by the fluoremetric method.

The average value for the hydrocarbons that was found was: 4.9 +_ 0.9 2 yg/l with a range of -3.7 to~13.6.

For chlorophyll a, it was 0.19 + 0.036

Vig/1 with a range jf 0.02 to 0.813.

The average hydrocarbon content was considerably lower than that found by

the author in the Baltic [7j , where the

saturated hydrocarbons alone had an average concentration of 8.9 +_ 2,0\ig/l.

Curves of estimation with significant

correlation (P under 0.05) were found

between hydrocarbon and chlorophyll

content with, linear, logarithmic,

quadratic, and hyperbolic equations.

The estimating equation that was decided

on was in the form: Y = a + b log (1 + C). This equation was felt to be the

most suitable for two reasons. It intersects the Y-axis when C = 0, thus

enabling an estimate to be made of the

amount of anthropogenic hydrocarbon

material present, and, secondly, in it

the rate of change in the hydrocarbon

concentration decreases greatly as the

chlorophyll concentrations become high.

This is to be expected, since a feedback

condition almost certainly exists between

the amount of phytoplankton and the

concentration of hydrocarbon material.

Although a larger phytoplankton population would result in a greater production

of hydrocarbon material, it should also

result in a larger amount of particulate

material upon which the hydrocarbons can adsorb C83 and then be removed from the

system by either sinking or grazing.

The estimating equation found was: Hydrocarbons (pg/1) = 1.7 + 41.1+5 log

(1 + Chlorophyll (yg/D)

r = 0.54

t = 3.0 0.005 <P< 0.01

^Y.X = + 3.6

N = 23 Where r is the correlation coefficient,

t is the result of a "t" test made on

it, ^Y.X is the standard error of

estimate, and N is the number of

samples. The correlation coefficient

is not very high, but the "t" test shows

that the probability of obtaining a correlation coefficient of that

magnitude due to chance is only possible

in less than 1 case out of 100. In - process as complicated as the one being

considered here, this is quite significant. The amount of material that is

presumably anthropogenic is 1.7 +_ S.^i yg/1. This is of course only a rough

estimate due to the high standard of

error, but it does suggest that anthropogenic material was present in the

waters tested. In the future more data

should be accumulated to make this

estimate more precise. A similar

analysis of the data from Northwest

Africa results in:

255
Hydrocarbons (relative units) =-0.1 + 8.41 log (1+C)

r = 0.67

t = 6.8 P << 0.001

sy.X = + 1.5

N = 58 The slopes in the two equations cannot

be compared due to different units used.

The two correlation coefficients do not

differ significantly » but due to the greater sample size, the value

off Africa is far more significant.

The amount of anthropogenic material

would be -0.1 +_ 1.5 yg/1, suggesting

that the waters there were free from

pollution. This is reasonable, since

upwelled water has been on the surface

for only a short period of time and is

unlikely to have been contaminated. In addition, sampling was done close inshore away from any tanker routes.

The average value for chlorophyll

that was found in the euphotic zone off

Northwest Africa was 3.5 yg/1. If one assumes no pollution and applies the

estimating equation found for the ocean

south of Canada, one would expect to find on an average about 27 yg/l of

hydrocarbon material off Northwest

Africa in the euphotic zone. Both these studies have indicated

that a casual relationship exists

between the hydrocarbon and chlorophyll

concentrations in the euphotic zones. Naturally one cannot assume that phytoplankton is the sole source of this

material. An increase in the phytoplankton population will also result in an increase in other members of the

ecosystem such as the zooplankton, and

these too might be introducing hydrocarbon material. Independent of this,

there also appears to be hydrocarbon

material in the ocean to the south of

Canada, which presumably is anthropogenic and is absent in the upwelled water

off Northwest Africa.

References

[ll Clark, R. C. Jr. and Blumer, M.

,

Limnol. Oceanogr. 12

,

79-87 (1967)

[2] Blumer, M. , Mullin, M. M. and

Guillard, R. R. L. , Mar. Biol.

6_j_ 226-235 (1970).

[3J Blumer, M. , Guillard, R. R. L.

,

and Chase , T .

, Mar. Biol

.

8

,

183-189 (1971).

[1+] Youngblood, W. W. , Blumer, M. , Guillard, R. L. , and Fiore , F.

,

Mar. Biol. 8^ 190-201 (1971).

r5l Zsolnay, A. , Deep-Sea Res. 20

,

923-925 (197377"^

["el Zsolnay, A., J. of Chromatography

90, 79-85 (1974).

[7] Zsolnay, A., Paper presented at 1973 Meeting of the International

' Council for the Exploration of

the Sea. CM. 1973/E:22 (1973).

[a] Zsolnay, A. , unpublished data.

[9^ Croxton , F . E . , Elementary

Statistics

,

Dover Pub . , New York

(1953) .

256
NBS Spec. Publ. 409, Marine Pollution Monitoring CPetroleum)

,

Proceedings of a Symposium and Workshop held at NBS, Galthersburg, Maryland, May 13-17, 1974 (Issued December 1974).

EFFECT OF AN OIL SPILL ON BENTHIC

ANIMALS IN THE LOWER

YORK RIVER, VIRGINIA

1

M. E. Bender

J. L. Hyland

T. K. Duncan

Division of Environmental

Science & Engineering

Virginia Institute of Marine Science2

Gloucester Point, Virginia 23062

U. S. A. Introduction

Although considerable study has been

centered upon intertidal organisms with

respect to their response to oil spills,

most investigations have been conducted

on exposed rocky intertidal habitats (1).

Few studies are available which describe

the response of benthic animal communities in mid-Atlantic estuaries and particularly in its largest estuary, Chesapeake Bay. This study documents both

from field survey data and laboratory

bioassay studies the effects of an accidental oil spill on the intertidal benthic

communities of the Lower York River,

Virginia.

Field Study

On 5 May 1971, a number of slicks of

oil (cracking residue thinned with No. 2 fuel oil to the consistency of No. 6 fuel

oil) washed onto the sand beaches and

Spartina marshes near the mouth of the

York River. To assess the effect that

this event had on the intertidal organisms of these beaches, a series of transects was established at three locations

in this area and sampled during July and

December of 1971, March of 1972 and April

of 1973. One transect of samples (station no. 2) was collected where a slick

came ashore, while two transects of

samples were taken in unaffected areas (stations no. 1 and no. 3). Station no.

1 is approximately 1.14 nautical miles

upriver from no. 2 and no. 3 is approximately 0.79 nautical miles downriver from

no. 2 (fig. 1).

The procedure on each transect involved making a subjective determination

of the width of the intertidal zone and

then setting up five equally spaced subThis study was supported in part by a grant from the Environmental Protection

Agency (150-80-EJ0)

.

2viMS Contribution No. 623.

Figure 1. Location of Sampling Stations

stations within this zone. A series of

ten samples was then taken to a depth of

15 cm with a plexiglass corer (0.0069 m2)

at each substation. The cores were

sieved through a 1.0 mm screen and the

material remaining on the screen was preserved in formalin that had been diluted

with seawater and returned to the laboratory for identification and enumeration.

During the study period, 94 species

of benthic organisms were collected. The

major fauna were distributed as follows:

29 species of polychaetes; 28 of crustaceans and 23 of molluscs.

To numerically describe the faunal

assemblages, several techniques of commu- nity structure analysis were employed.

These included species richness, evenness,

information theory diversity, and the use

of Sorenson's quotient of similarity (2).

The number of species, individuals,

and values for richness, evenness and

diversity calculated on the samples during the study are tabulated in table I. Figures 2 and 3 show the change in richness and diversity as a function of time.

Figure 4 graphically depicts the change

in Sorenson's similarity quotient as a function of station comparisons and time.

The effect of the spill is most evident when comparing numbers of species

or species richness. The control stations

averaged 33 species in July after the

spill while the spill station had only 14. The effects of the spill were prolonged

through the next two sampling periods,

in December 1971 and March 1972.

Recovery in terms of both species richness and faunal similarity was shown in

the April 1973 study period. However,

the number of individuals remained lower

at the spill station than at the control

stations, suggesting that complete re- covery had not yet occurred. The groups

257
Table I. Community Composition Parameters

Station 1 Station 2 Station 3 7-71 12-71 3-72 4-73 7--71 12-71 3-72 4-73 7-71 12-71 3-72 4-73

No. Indi. 482 536 300 231 88 107 144 153 611 2481 1757 3753

No. Sp. 32 34 35 21 14 19 13 22 34 60 46 37

Richness 5.02 5.25 5.96 3.67 2 90 3.85 2.41 4.17 5.14 7.55 6.02 4.39

Diversity 3.02 3.21 3.63 3.00 3 28 3.21 1.85 3.25 3.02 4.04 3.29 2.67

Evenness 0.60 0.63 0.71 0.68 0 86 0.76 0.50 0.73 0.59 0.68 0.60 0.51

I

' ' II I I I I > I I I

I I I I I I MAY JUL DEC MM DEC APR h 1971 1 1974 |_|973_j

DATE

12/71 3/72

(l-3)0-2Ha-3) (1-3) (1-2) (2-3) (1-3) (1-2) (2-3) (1-3) (1-2) (2-3) STATIONS

Figure 2. Species Richness Figure 4. Sorenson's Similarity Quotient

4.0

ts.o2.0

MAY JUL DEC

I 1971 h

I

I >

I

I I—I I I I I—I

I

I I I—[ I I

-1972- OEC APR 4—1973—1

Figure 3. Species Diversity

duct acute bioassays with the oil and

attempt to relate the toxicities to the

effects observed in the field. Unfortunately, no samples of the oil spilled had

been taken; therefore, it was decided to assay Bunker C because of its close

resemblance to the oil spilled and because

of its extensive use as vessel, industrial and utility fuels.

The test organisms included Spio - chaetopterus costarum oculatus (PolycKaetaj, Nereis succTnea (Polychaeta)

,

Nassarius obsijTetus (Gastropoda) , Modio- lus demissus (Bivalvia), Edotea triloba

(Isopoda), Gammarus mucronatus (Amphipoda) and Pagurus longicarpus (Decapoda)

.

The organisms were chosen because they

appeared as York River dominants (3),

(4) and because they represented major

taxonomic divisions of York River intertidal macrofauna.

most seriously affected by the spill were

the crustaceans and polychaetes.

Laboratory Studies

After preliminary analysis of the

field data showed a significant effect

of the oil on intertidal organisms in the

Lower York River, it was decided to conOnly the toxicity of the water-accommodated components of Bunker C rather

than the residue, was assessed in the

study. The dosing apparatus used was a closed continuous flow system, where

pumps delivered various dilutions of an equilibrated oil in water solution to flasks in which the test animals were

placed. Quantitative estimates of the

258
oil were made using infrared spectroscopy (5).

The test organisms were subjected

to five concentrations of oil with a control. The tests were conducted for

48 hours at salinities ranging from 12 to 18^0. Duplicate tests were conducted

with each organism. The total dissolved

organic content of the equilibrated oil

and water solution was 5.53 ppm. Frankenfeld (5) previously reported only 1.9

ppm water extractable organic compounds

from a No. 6 fuel oil. The difference

between the two results may be that during his study, solutions of oil and

water were not agitated. In this study

mechanical agitation was used. However,

no "solutions" were tested before all

visible oil had appeared to float to the

surface

.

In the replicated experiments

neither N. obsoletus , E. triloba, N. succinea, nor M. denissus showed mortality which couTd be attributed to the

presence of oil, while in all assays G. mucronatus , P. longicarpus and S^. costa - rum oculatus displayed patterns of mortality from which TL50 values could be

determined, '^he 48 hour TL50 values

were 0.42 ppm for G. mucronatus , 0.62

ppm for P. longicarpus and 4.92 for S^. costarum oculatus . Further details concerning the bioassay tests can be found in Hyland (6).

Discussion

The four species which were not

affected by accommodated oil in the

laboratory also did not reveal population

depressions following the oil spill in

the river. The tolerance displayed by

N. obsoletus and M. demissus may reflect

a general resistance of molluscs to acute oil toxicity as suggested by

Mironov (7) and Moore, Dwyer and Katz (8). It should be mentioned, however, that

molluscs may be susceptible to other

adverse effects, e.g. as Scarrat, Sprague,

Wilder and Zitko (9) have demonstrated

the ability of M. modiolus to concentrate

various fractions of Bunker C. In addition the toxicity of dissolved oils

should be tested for larval molluscs before such a generalization should be

made

.

It is not understood why Edotea was

tolerant to the oil, since the two other

crustaceans tested were quite sensitive,

both having TLso's under 1 ppm. Unfortunately, our field sampling techniques

did not allow for the capture of the

hermit crab (P. longicarpus ) which was

shown to be tKe most sensitive species.

Spiochaetopterus for which acute toxicity

was shown exhibited the most drastic

population reduction in the field study.

Species richness and faunal similarity appeared to give a better indication

of the effects of the oil than did the

informational diversity calculations.

References

:

(1) Boesch, D. F. and Hershner, C. H. The Ecological Effects of Oil

Pollution in the Marine Environment,

in Oil Spills and the Marine Envir- onment. Ballinger, Cambridge, Mass

.

(1974).

(2) Diaz, R. , Bender, M., Boesch, D.,

Jordan, R. Water Quality Models

and Aquatic Ecosystems Status,

Problems and Prospectives , in Models

for Environmental Pollution Control , Deininger, R. A., Ed. Ann Arbor

Science, Michigan (1973).

(3) Orth, R. J. Benthic Infauna of

Eelgrass, Zostera marina , Beds,

M.S. Thesis, University of Va. 79

p. (1971).

(4) Boesch, D. F. Distribution and

Structure of Benthic Communities

in a Gradient Estuary. Ph.D. Thesis.

College of William and Mary. 120 p.

(5) Frankenfeld, J. W. Factors Governing the Fate of Oil at Sea; Varia- tions in the Amounts and Types of

Dissolved or Dispersed Materials

during the Weathering ProcesT^ ^Pro- ceedings of Joint Conference on Prevention and Control of Oil Spills,

Wash. D. C. pp. 435-495 (1973).

(6) Hyland, J. L. Acute toxicity of No.

6 Fuel Oil to Intertidal Organisms

in the Lower York River, Virginia.

M.S. Thesis, College of William and

Mary. 57 p. (1973).

(7) Mironov, 0. G. The Effect of Oil

and Oil Products Upon Some Molluscs

in the Littoral Zone of the Black

Sea. Zool. Zh. 46:134-136 (1967).

(8) Moore, S. F., Dwyer, R. L., Katz,

S. N. A Preliminary Assessment of

the Environmental Vulnerability of

Machias Bay, Maine to Oil Supertankers. Report No. MITSG 73-6. 162 p. (1973).

(9) Scarrat, D. J., Sprague, J. B.

,

Wilder, D. G., Zitko, V. Some

Biological and Chemical Investigations of a Major Winter Oil Spill on

the Canadian East Coast. Int. Counc.

for the Exp. of the Sea, Fish. Imp.

Comm. CM 1970/E 14. (1970).

Key Words: Acute toxicity; Benthic

animals; Oil; Response

259
V
NBS Spec Publ. A09, Marine Pollution Monitoring (Petroleum), Proceedings of a Symposium and Workshop held at NBS. Gaithersburg. Maryland. May 13-17. 1974 (Issued December 1974).

MARINE POLLUTION BY

CARCINOGENIC HYDROCARBONS

James B. Sullivan

Center for Science in the Public Interest

1779 Church Street, N.W. Washington, D.C. 20036

Polycycllc aromatic hyd

associated with the use of p coal, the burning of refuse,

ductlon of coke have caused

as an atmospheric pollutant

Increased Incidence of lung

are also being studied In ci some foods, soil, and water,

nation of seafood due to oce

tlon, however, has received

attention

PAH Content of Petroleum

rocarbons (PAH)

etroleum and

and the progreat concern related to cancer. PAH's

garette smoke,

PAH contamlan oil polluvery little

The 11 beglnnlngso

clnogenlc c products

analytical

over 325°C

studied as According t appreciably

above 354oc

terature

f an adeq

ontent of

Partly be

technique

have not

the lower

o Horton

higher 1 than in

contains

uate stU' petrole

cause of

s , compo

been as boiling

et al . , n fractl

crude st

only the

dy of the car- um crudes and

Inadequate

nents boiling

thoroughly

fractions

PAH are

ons boiling

ocks (1 )

Carruthers and Douglas in 1961 isolated 1 , 2-benzanthracene from uncracked

fractions of Kuwait petroleum. Also isolated in Kuwait crude were chrysene,

fluorene , phenanthrene , and dlbenzthlophene (2). Graf and Winter made quantitative measures of benz(a)pyrene (BP) in

crude oils from the Persian Gulf, Libya,

and Venezuela. Levels were 400, 1320,

and 1,600 pg/kg respectively (3).

Crude oil PAH are estimated to be on

the order of 1 percent of total crude. A Bureau of Mines analysis of a Gach Saran

crude found PAH in the 370-535 °C range to be 3-54 percent of the total crude (4).

The amount of carcinogenic hydrocarbons is Increased by refining processes

that involve catalytic cracking and reforming. The following table shows the

aromatic increases from representative

operations (5 ) : Process

Cat. cracking

Gulf Res . Co

Cat. reform.

Houdry Air Pr.

Cat. reform.

Charge

Kuwait Gas

Oil

Naptha

Arabian

% before Rafter

22.3 'iO.O

18.8

10.5

56.4

66.2

Esso Research and Engineering Co. analyzed commercial grades of gasoline and

found BP content ranging up to 3»120 pg/kg.

Nationwide composite premium contained

i|80 Mg/kg while regular contained 212

yg/kg (6).

Another source of high PAH is spent

petroleum products . The BP content of

unused motor oil was 26 pg/kg as compared

with 5,800 Mg/kg BP in the oil after being

used in an engine for about 1,400 miles(7).

Estimate of PAH Discharged into the Ocean

The best estimates indicate that over

half of total petroleum discharge Into the ocean is petroleum product, not crude oil.

According to Porricelll (8), marine operations (excluding offshore operations)

account for 47.1 percent of total petroleum

discharged. The American Institute of

Merchant Shipping estimates that ten percent of world tanker trade is light product (9). Thus, marine operations with

light product probably account for 4.7

percent of total marine pollution.

(This estimate is conservative. Most

transport estimates consider international

trade only and neglect Intracoastal trade.

For U.S. petroleum shipping, for example,

intracoastal trade amounts to approximately 43 percent of all shipments (10).

A good deal of this intracoastal trade is

product. Excluding intracoastal trade

from total petroleum shipping calculations

gives the result that product accounts for

only 46 percent of total transport; including Intracoastal trade causes that figure

to jump to 55 percent. This would raise

the percentage of marine pollution caused

by product .

)

According to Porricelli, refineries,

petrochemical plants, and industrial

machinery, if we assume they discharge only

product, add 21.4 percent of product to the

4.7 percent by marine operations. Motor

vehicle pollution, all product, adds

another 29.4 percent making 55.5 percent

of all petroleum discharge into the ocean

that is product.

If we use Porricelli 's estimate of

5 million tons as total petroleum input

and if we assume that all crude has a BP content of 400 to l600 pg/kg, that non- automotive product is l600-6400 yg/kg,

and that motor vehicle discharge is 5800

yg/kg, we get annual BP input of 10 to

20 metric tons.

Comparison of BP in Seafood and in Other

Foods

Numerous reports have been published

on the presence of carcinogenic PAH in

marine and fresh waters as well as in a variety of natural and processed food

products. The following estimates that

are unfootnoted come from reviews by

261
Andelman and Suess (11), and ZoBell (12). Is Oily Taste Any Protection?

The general range of carcinogenic

PAH in ground water and treated surface

water is between 0.001 and 0.025 Pg/1. BP was found in lettuce at a maximum

concentration of 12.8 yg/kg. FDA surveys

of vegetable oils have found BP levels

from 0.4 to 1.5 yg/kg (13). Another study

found BP content as high as 48.4 yg/kg in

cocoanut oil.

Grimmer found that BP in 23 samples

of cereal grain varied from 0.2 to 0.4

yg/kg. Water extracted from 1 kilogram of

tea contained about 4 yg of BP; 11 samples

of coffee contained hardly any hydrocarbons at all (although BP has been found

in roasted coffee beans).

Lijlnsky and Shubik report 8 yg/kg

of BP in smoked salmon, 6 to 10 yg/kg in

barbecued ribs and charcoal broiled steaks,

and Gorelova and Dikun found up to 10.5

yg/kg in home-smoked sausages.

Concentrations of BP in marine

animals vary quite widely from nil to over

2000 yg/kg:

Sample

Cod fish

molluscs

holothurians

mussels

crustaceans

mussels

molluscs

sardines

various

fish

invertebrate

shrimp

mussels

oysters, etc

oysters

oysters

mussels

oysters

holothurians

fish & crus

fish & shell

fish

oysters

oysters

Location

Greenland

Arctic Ocean

Bay of Naples

Italy, Adriatic

Coast

s

" Prance

Prance, Atlantic

Coast

Prance, Channel

Coast

Prance, Toulon

French Coast

Alabama

Virginia

BP content

15

60

nil

18-55

nil to 11-540

2.4

65

nil-900

230

Thus, the amount of BP in s appreciably higher than amounts

marine food. The higher values

in marine foods are undoubtedly

to petroleum contamination from

ing sources . The presence of re high levels in the Arctic Ocean

Greenland indicate possibly high

of BP in the entire world ocean. Indicates a strong need to monit

levels, especially near major so pollution and near fishing groun

nil-2200

nil-90

0.4-3.5

yg/doz.

70-112

16-22

1- 70 up to 2000

nil-400

3-155

242- 6 eafood is

in non- found

due

neighborlatlvely

and off

levels

This

or PAH

urces of

ds

The question arises as to whether

petroleum contamination of seafood produces an oily taste that would prevent

anyone from eating that seafood. Only a relatively small fraction of petroleum has

a pronounced odor or taste. Moreover,

marine animals removed from contaminated

areas may not purge themselves of PAH. Blumer and his co-workers at Woods Hole

suggested that petroleum hydrocarbons may

persist for long periods after contamination, perhaps for the lifetime of the

animal (l4).

Two studies sponsored by the American

Petroleum Institute are somewhat

inconsistent with Blumer' s results. The

first, by J.W. Anderson found that maintenance in clean water for periods of from

24 to 52 days is sufficient to cleanse the

tissues of detectable levels of hydrocarbons (15). The second, by Battelle Labs

also found rapid (within two weeks) purging

by oysters of Kuwait Crude oil (l6).

Lee et^ al. studied the uptake and discharge of four toxic or carcinogenic hydrocarbons by the marine mussel Mytilus edulis . The mussle did not metabolize any of the

compounds and, while transfer of the mussel

from contaminated to fresh water did cause discharge of most of the hydrocarbons,

significant amounts (1 to 400 yg/mussel)

remained two weeks after the transfer (17).

Teal and Stegeman at Woods Hole found

similar hydrocarbon discharge behavior in

oysters (l8). No. 2 fuel oil was accumulated by oysters after a 49 day exposure at a rate dependent on their lipid weight and was then partly discharged upon transfer of

the animals to fresh sea water. The

residue of accumulated hydrocarbons

amounted to over thirty times that found in

the oysters prior to exposure; the authors

suggest the stored hydrocarbons represent

a new equilibrium concentration of hydrocarbons in the organism or may be retained

in a stable compartment.

Thus, while knowledge about the persistence of PAH in contaminated seafood is

far from complete, it is clear that relying

on oily taste in seafood as a danger warning is not warranted by the studies con- ducted on this issue. Only objective

chemical analysis and not subjective taste

can reveal the presence of some carcinogenic hydrocarbons. Again, this stresses

the need for monitoring of PAH levels in

fishing areas and in contaminated offshore

areas . References :

(1) Horton, A.W. et al . , Amer . Chem. Soc

Dlv. Petrol. Chem. Preprints b(4),

C59-C65 (1963)

(2) Carruthers, W. and A.G. Douglas,

262
Nature , 192 , 256-257, 1961 (H)

(3) Graf, W., and C. Winter, Arch . Hyg . Bakt . , 152, 289-293, 1968 (12)

(it) Dooley, J.E., et al . , U.S. Dept.

of Interior, Bureau of Mines Report

of Investigations 7770, 1973 (13)

(5) 1972 Refining Processes Handbook,

Hydrocarbon Processing , 51j 9* 1972 d'*)

(6) Gasoline Composition and Vehicle

Exhaust Gas Polynuclear Aromatic (15)

Content, NAPCA Contract CPA-22-69-56

,

Products Research Division, Esso Res. and Engineering Company, 1970.

(7) Graf and Winter, Op., cit. (16)

(8) Porricelli, J.D., et al, , Trans. Soc.

Naval Architects and Marine Engr . , - (17)

79, 1971 . (9) American Institute of Merchant (lo)

Shipping, "Working Paper on Technical

and Economic Considerations of NATO

Resolutions to Eliminate Intentional

Discharges of Oil in the Sea," 1971.

(10) "Waterborne Commerce of the U.S.,

1971," U.S. Army Corps of Engineers.

Andelman, J.B. and M.J. Suess,

Bull. Wld. Hlth. Org . , t3 , 479-508 , 1970

ZoBell, C.E., Proc. Joint Conf. on Prevention and Control of Oil Spills,

1971, (API/EPA/USCG) , 441-451

Howard, J.W. et_ al . , Jour. Ass. Off . Anal. Chem . 49, 123^-1244,1966

Blumer, M. , and J. Sass, WHOI

Tech. Report 72-19, 1972

Anderson, J.W., Background Paper,

NAS Workshop on Inputs, Fates, and

Effects of Petroleum in the Marine

Environment, 690,1973

Vaughan, B.E., Contract 212B00439,

American Petroleum Institute, 1973

Lee, R.P. et_ al. , Science , 177 , 344-346,1972

Teal, J.M. and J.J. Stegeman,

Background Paper, NAS Workshop on Inputs, Fates, and Effects of Petrol,

in the Marine Environment, 571, 1973

263
s
AUTHOR INDEX (Contributed Papers)

A

Ahmadjian, M 91

Ahmed, A. M 109

Anbar, M 229

B Bean, R. M 127,217

Beasley, M. D 109

Bender, M. E 257

Bieri, R. H 149

Blaylock, J. W 217

Boyd, R. N 117

Brooks, J. M 171

Brown, C. W 91 Brown, R. A 131

Bruce, H. E 181

Burns, K 163

Butler, J. N 75

C Cawlfield, D. E 237

Chang, W. J 85

Chesler, S. N 197

Clark, R. C. Jr 189,209

Colton, J. B 243

Conomos, T.J 97

Cram, S. P 197

Cretney, W. J. 175

Curtis, M 79

D DiSalvo, L. H 213

Donovan, D. J 201

Dow, R. L 201

Dryfoos, R. L 243

Duncan, T.K. » 257

Dwivedi, S. N. » 101

E Efromson, A. C 109

Ehrhardt, M 221

Elliott, J. J 131

Enagonio, D. P 197

F Farrington, J. W 163,167

Feldman, M. H 237

Finley, J. S 209

G Gordon, D. C. Jr 113

Guard, H. E 213

Gump, B. H 197 H Hagstrom, k 251

Heinemann, J. „ 221

Hertz, H. S 197

Hites, R. A 109

Hornig, A. W. ...... . 135

Hufford, G. L 83

Huggett, R. J 149

Hunter, L 213

Hurst, J. W. Jr 201

Hyland, J. L 257

J Jadamec, J. R 85

James, B. M. „ 233

Jeffrey, L. M 233

Jiang, L 201

Justchak, A. A 245

K Kawahara, F. K 145

Keizer, P. D 113

Kennedy, E. A 233

Kim, H. H 95

Kinnear, B. S 243

Knapp, K. D. 243

L La Roche, G . 249

Lewis, B. W. 149

Losser, Go , 149

Lynch, P 91

M

May, W. E 197

Mayo, D. W 201

McAuliffe, CD 121

McGowan, W. E 83

Medeiros, G. C. . . . o . .. 167

Morris, B. F. ...... . 75

N

Notini, M 251

0

Oradovski, S. G 245

P Parker, P. L „ . . 163

Parulekar, A. H 101

Pequegnat, W. E 233

Pierce, R. H. Jr. 161

Q

Quinn, J. G. 163

265
s Sackett, W. M. . 171

Saner, W. A 79,83

Schwemmer, G. K. 95

Scolnick, M. E 229

Scott, A. C 229

Searl, T. D 131

Sherman, K 243

Simonov, A. 1 245

Straughan, D 183

Sullivan, J. B 261

T Teal, J. M 163

Traxler, R. W 161

V

Vos, A 233

W

Wade, T. L 163

Walker, A. L 149

Warner, J. S 195

Wasik, S. P 117

Wildung, R. E 217

Winters, J. K 163

Wong, C. S 175

Wright, D. E 93

Wright, J. A 93

Y

Yolken, H. T 157

Z Zahka, J. G 89

Zsolnay, A 119,255

266
KEY WORD INDEX

Entries were taken from the key words given by authors

of the contributed papers printed herein. Reference is

only to first author of each paper. This index is not

exhaustive; however, it should serve as a subject guide.

Airborne sensor

- Schwemmer

Analysis

discriminant function

- Kawahara

infrared

- Kawahara

minor components

- Kawahara

Analysis of tar

- Butler

Analytic methods

- Clark

- Hornig

Aromatic hydrocarbons

- Bruce

- Gordon

- Hertz

- Warner

- Wasik

- Zsolnay

Baltic littoral community

- Notini

Beach bias

- Saner

Beach time constant

- Saner

Biological effects

- Sackett

Biological productivity

- La Roche

Boston Inner Harbor

- Ahmed

Chemical baseline

- Hertz

Chlorophyll

- Zsolnay

Chromatography, gas

- Bean

- Bieri

- Brown

- Bruce

- Clark

- Hertz

- Kawahara

- Mayo

- McAuliffe

- Medeiros

- Traxler

- Warner

Chromatography, liquid

- Blaylock

- Brown

- Clark

- Cretney

- Zsolnay

Computers

- Bieri

- Kawahara

Contamination

- Bruce

- Clark § Finley

Criteria

- Traxler

water quality

- La Roche

Crude oil suspensions

- Bean

Distribution coefficient

- McAuliffe

Drift, nontidal

- Conomos

Drifters

seabed

- Conomos

surface

- Conomos

Electrolytic stripping cell

- Wasik

Environmental monitoring

- Yolken

- Feldman

Environmental Surveys

- McAuliffe

Equilibration

- McAuliffe

Equilibrium value

- Saner

Estuarine circulation

- Conomos

Fluorescence

- Cretney

- Gordon

Filtration of unsoluble oil

- Bean

Fuel oil. No. 2

- Bieri

267

Head-space

- Wasik

Hydrocarbons

along shipping routes

- Brown

carcinogenic

- Sullivan

fossil

- Bieri

general

- Clark

- Medeiros

- Sackett

- Zsolnay

in atmosphere

- McAuliffe

in Gulf Stream

- Zsolnay

in Kiel Bight

- Ehrhardt

in marine organisms

- Bruce

- Ehrhardt

- Farrington

in ocean water

- Brown

in sea water

- Gordon

in water

- Bean

- McAuliffe

measurement of

- Brown

partitioning of

- McAuliffe

petroleum

- Clark § Finley

- Straughan

profile

- Hunter

"sniffer"

- Sackett

tissue

- Hunter

types

- Blaylock

- McAuliffe

type determination by IR,

by spectrophotometry

- Bean

Identification

- Kawahara

Infrared oil film monitor

- Wright

Infrared quantiation

- Ahmed

Infrared reflectance

- Wright
Infrared spectroscopy

- Brown

Intercalibration

- Medeiros

Isoprenoids

- Mayo

Laser

- Schwemmer

Lipids

in ocean water

- Brown

along shipping routes

- Brown

Luminescence

in oils

- Hornig

low temperature

- Hornig

molecular

- Hornig

spectroscopy

- Hornig

Marine organisms

- Bruce

- Clark

- Ehrhardt

- La Roche

- Medeiros

- Warner

Marine pollution

- Yolken

Neuston, neuston net

- Butler

- McGowen

- Sherman

North Atlantic

- Butler

- Simonov

Ocean pollution detection

- Wright

Oil absorption

- Mayo

Oil classification

- Bender

- Hornig

Oil detection

- Zahka

Oil drilling, ocean platforms

- Sackett

Oil film detection

- Wright

Oil fluorescence

- Hornig

Oil Fluorosensor

- Schwemmer

Oil Identification

- Chang

- Hornig

Oil pollution

- Clark

- Farrington

- Gordon

- Mayo

- Medeiros

- Sackett

- Simonov

- Sullivan

- Wright

Oil recovery

- Zahka

Oil sampling

- Brown

- Chang

- Zahka

Oil seepage

- Straughan

Oil spills

- Brown

- Conomos

- Kawahara

- Notini

Oil weathered

- Mayo

Open ocean

- McGowen

Organisms

benthic

- Bender

- Mayo

- Straughan

test

- La Roche

Pacific North East

- Cretney

Paraffin residual patterns

- Clark

Partition coefficient

- Wasik

Particulate matter

- Traxler

Petroleum

- Butler

Petroleum analysis

- Traxler

Petroleum contamination

- Clark

Petroleum- in-water analys

- Ahmed

Phosphorescence

in oils

- Hornig

Prince William Sound

- Hertz

Remote detection, sensing

(see also infrared) - Hornig

- Schwemmer

- Wright

Sampling

- Butler

- Gordon

- Straughan

Sampling errors

- Ahmed

San Francisco Bay

- Conomos

- Hunter

Sargasso Sea

- Butler

Sargassum

- Butler

Scot columns

- Mayo

Sea water

- Wasik

Sediments

asphaltenes in

- Blaylock

benthic

- Straughan

general

- Clark

- Mayo

hydrocarbons in

- Blaylock

- Hunter

monitors

- Hunter

organic

- Blaylock

sampling

- Bruce

Selective membrane

- Zahka

Silica gel fractionation

- Warner

Sorbents

- Chang

Specific compound identification

- Bieri

268
Spectroscopy

fluorescence

- Cretney

Spectrometry, mass

- Anbar

- Bieri

- Blaylock

- Warner

Standard Reference Materials

- Yolken

Standards

chrysene

- Cretney

Standards and intercomparison criteria

- Traxler

Surfactants

- Chang

Tar

- Butler

- Jeffrey

pelagic

- Jeffrey

Tar balls

- Feldman

- Jeffrey

- McGowen

- Traxler

asphalteries of

- Jeffrey

in Caribbean

- Jeffrey

in Gulf of Mexico

- Jeffery

in Gulf Stream

- Sherman

sulphur of

- Jeffrey

Test systems

model

- Notini

Tissue analysis

- Clark § Finley

Tissue extraction

- Warner

Toxicity

- Bender

- Notini

Trace analysis

- Hertz

Water accommodate

- Bieri

Water surface monitoring

- Wright

269
I

I

I
REPORT

of the

WORKSHOP ON MARINE POLLUTION MONITORING

held at

Gaithersburg , Maryland, USA

(16-17 May 1974)

271
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272
INTRODUCTION

The International Symposium and Workshop was prompted by the recognized

need to communicate and exchange ideas and results, on an international basis,

which reflect the status of current methodology for making measurements of

petroleum and petroleum products in the marine environment. Such needs arose

as the Intergovernmental Oceanographic Commission and the World Meteorological

Organization decided to establish an operational Pilot Project for Marine

Pollution Monitoring which was initially to focus on petroleum hydrocarbons

within the framework of the Integrated Global Ocean Station System (IGOSS)

programme. The outline of the Operational Plan on the above Pilot Project on Marine Pollution Monitoring and implementation programme were prepared by the

Joint lOC/WMO Planning Group for IGOSS at its second session (13-17 August

1973) and subsequently endorsed by the Eighth Session of the IOC Assembly

(Res. VIII-20) , and the 25th session of the WMO Executive Committee (Res. 14).

The objectives of the Workshop were: (a) to provide scientific and

technical advice, based mainly on information supplied by the Symposium, as to

methodology (observation and reporting, sampling, sample preservation, analysis,

standards criteria, data handling) to be used or initiated during the Pilot

Project, and also to identify future studies needed to expand the Pilot

Project; (b) to recommend technical assistance programs and training and

education projects that would provide pertinent support to developing countries

to enable them to establish marine pollution monitoring activities.

Results of the discussion on the above matter as well as conclusions and

recommendations on the Operational Plan for the Pilot Project and further

studies and actions required for its development are contained in this report.

273
GENERAL CONCLUSIONS ON THE PILOT PROJECT ON MARINE POLLUTION MONITORING

When reviewing the Operational Plan on the Pilot Project on Marine

Pollution Monitoring and results of the discussion at the Symposium on marine

pollution (petroleum) monitoring, the Workshop agreed that the basic objectives

for the Pilot Project were the following:

- To initiate and expand an internationally coordinated programme for

marine pollution monitoring, initially in selected areas, in order to acquire

and exchange among nations intercomparable data for making periodic assessments

of the state and degrees of contamination of the marine environment by oil and

petroleum constituents

- to establish the necessary organizational machinery required for

further development and expansion of marine pollution monitoring.

Taking into account the fact that a significant period of time will be

required for nations to prepare themselves for appropriate use of the

recommended procedures and methods within the Pilot Project, as well as to

train personnel on procedures for sampling, preservation and analysis, to

prepare national guides and instructions, the Workshop proposed to start

implementation of the operational phase of the Pilot Project in accordance with

the recommended procedures on January 1, 1975 . Therefore the Preparatory

Implementation Phase to complete the required preparatory work should be

conducted within the period of time June 1974 to January 1975.

The Workshop also proposed that one year after the initiation of the work,

namely January 1976, an evaluation of progress of the Pilot Project should be

conducted with the view to its further development. To this purpose, the

second Workshop of national coordinators and laboratory directors as well as data managers should be convened in January 1976.

The Workshop considered existing and planned national regional marine

pollution monitoring programmes and took into account recommendations of the

4th Session of the IOC Group of Experts on Oceanographic Research as it relates

to IGOSS (April 1974), on the expansion of the area for the Pilot Project.

The Workshop recommended inclusion, in addition to the areas recommended by

the IPLAN-II for the Pilot Project, the Norwegian Sea, the ocean areas around

Japan, and the northern part of the Indian Ocean.

Other conclusions and recommendations supplied by the Workshop are given

in the following:

274
OIL SLICKS , TAR BALLS AND PARTICULATES

SAMPLING METHODS AND TECHNIQUES: ANALYTICAL METHODS

Chairmen: Mr. T. Thompson

Mr. M. Gruenfeld

Rapporteur: Mr. B. Thompson

General Comments on the Operational Plan of the Pilot Project

The sessions, in light of present technological capabilities, were in

general agreement with the Operational Plan. Some changes in the sampling,

analysis and reporting procedures were recommended and it was strongly urged

that the projected analysis scheme be simplified and that a beach monitoring

program be considered in addition to the visual and Neuston net means of

acquiring data.

Methodology

(1) Visual - The sessions considered that the use of Polarizers in

detecting oil slick was very effective, both from ships and aircraft.

(2) Neuston nets (Tar Balls) - The sessions supported the collection of

information on Tar Balls through the use of Neuston nets and suggested

several sampling procedure changes that should improve the data collection.

The recommended changes are:

(a) Tow at speeds that permit the sampler to ride smoothly on the

ocean surface (3-8 kts).

(b) Where suitable equipment is available, a flow meter should be

employed to estimate the water scavenged.

(c) Sample during day or night, recognizing that daytime sampling

will reduce the amount of zooplankton collected.

(d) Where possible, tow the net on the lee side of the vessel, and

avoid heading into the wind (to minimize towing along or between

windrows)

(3) Tar ball sampling on beaches - It was agreed that this method would

prove useful as a complement to Neuston nets tows, in particular in areas where few research vessels are available. It was suggested that locations

along the African coast would be appropriate for beach monitoring of oil

spills along the tanker routes. Such sampling would have to be carried out

over an extended period (at least a year) to cover seasonal variability

(upwelling, monsoon, etc.). The Pilot Project should include a beach

monitoring program at the earliest practicable date. It is recommended that

the draft programme specifications given in Annex I should be reviewed by

appropriate experts prior to issuance as program guidelines.

275
(4) Sample preservation - The session felt that the addition of sodium \ azlde (NaN3) to tar ball samples Is not desirable. Refrigeration, as well as i freezing, should be suggested In the operational plan. The sentence, "Screw

caps should be lined with tin foil when teflon liners are not available"

should be added to paragraph 3, Appendix II of the Operational Plan.

Data Handling

Forms for reporting

The Workshop suggested some modifications to the format (s) as given

In the Operational Plan for the Pilot Project and recommended that the Joint

Task Team refine the reporting forms and Include these Incorporations in the

final version of the Operational Plan for the Pilot Project.

Complementary environmental data should be reported in the adopted

IGOSS code forms, e.g., BATHY and TESAC code. This would ensure that all

parameters would be compatible and the observation techniques fully explained.

The log form for sampling and reporting of particulate petroleum

residues (tar balls) should be revised to include all the information

contained in the recommended bottle label. As a minimum, an identification

number, identifying the sample on the log, should be clearly marked on the

bottle and the bottle top as well. Ideally, a label and log form should be

used

.

Data Collection

The sessions recommended that the National Coordinators arrange that all

forms be forwarded to the IGOSS Responsible National Oceanographic Data

Center (RNODC) for generation of statistical summaries and archival purposes.

The lODE ad hoc Group on IGOSS Data Archiving and Exchange should be

Instructed to prepare a supplement for the Manual on IGOSS Data Archiving and

Exchange, outline Marine Pollution Monitoring Pilot Project archival arrangements .

Supporting Studies for Expansion and Further Development

Guides and Manuals

It was further recommended that the Operational Plan be used by

participating nations as instructions, or guides, for use during the first

stage of the Pilot Project. International guides and instructions will be

considered after the first stage. Such guides and manuals should be simple

and, as far as possible, in conformity with the existing WMO and IOC guides

and manuals.

New Techniques - Various new techniques and developments were presented

at the session. It is proposed that they be kept under review by the Joint

lOC/WMO IGOSS Group of Experts and further considered when they become

operational. These Include:

276
(a) Remote sensing techniques

Multispectral Scanners (MSS)

Infrared and Ultraviolet Oil Monitors

Airborne Laser Systems

Microwave Instruments

(b) Improved simplified surface collection and observation

techniques

Platforms

Fishing vessels were judged as useful platforms for, in particular,

visual observations. It was proposed that National Coordinators encourage

the participation of an increasing number of ocean going fishing vessels in

the Pilot Project.

277
I

t

i

I
Annex I to Report on Oil Slicks, j: Tar Balls, and Particulates

Sampling Methods and Techniques

:

Analytical Methods

Tar Sampling on Beaches '

Selection of Area

(1) Minimum of human activity;

(2) No local sources of petroleum pollution;

(3) Uniformity of shoreline (no breakwaters or cuts)

;

(4) Sandy beach;

(5) Gentle slope should be present but not so as to make distance from

high to low tide mark too large for practical sampling.

Size of Sampling Zone

An area 6 meters (20 linear feet) along the beach and from backshore to

low tide mark across the beach.

Frequency of Sampling

Every 9th and 10th days - In this way the 9th day sampling will represent

9 days of tar accumulation and the 10th day samplings will represent one day

of tar accumulations.

Duration i

One year, to commence at any time of the year.

Number of Samplings

Two sets - 35 samplings each (one set of 35 day 9; one set of 35 day 10).;

Sampling Procedure

Stake out area. Clean off all debris from backshore to waterline prior to

sampling. Sample only at or near time of low tide. Pick up all visible

solid and semi-solid pieces of tar on surface of beach only. Weigh and record

recoveries. The Workshop suggested some modifications to the format (s) as given in the Operational Plan for the Pilot Project and recommended that the i! Joint Task Team refine the reporting forms and include these incorporations in

the final version of the Operational Plan for the Pilot Project.

il

ii

II

i!

27Q

:i

II
I

I V
PROCEDURES FOR SAMPLING AND REPORTING PETROLEUM HYDROCARBONS

DISSOLVED AND DISPERSED IN SEA WATER

Co-chairmen: Drs. E. Levy and M. Ehrhardt

Rapporteur : Dr. A. Zsolnay

Sampling

It has been agreed that, in the initial stage of the Pilot Project, water

samples would be collected from one meter depths. Uncontaminated water

samples are readily collected by the following method

50 ml of hydrocarbon-free carbon tetrachloride! are placed in a clean2 brown-glass bottle (3-4 litres) . The bottle is sealed with

a screw cap lined with degreased tin foil. This preparation should

be carried out by the participating laboratory prior to the field

work. Immediately before samples are taken, the bottle » with cap removed,

is placed in the weighted holder (cf. Fig. 1).

While the ship is still moving slowly forward, the assembly is

thrown overboard from the bow and as far as possible away from

the ship. The bottle will immediately sink and fill with water.

Upon retrieval, some water is spilled (sufficient to allow for

possible thermal expansion) out of the bottle. The cap is

securely fastened and the bottle stored m^ay.

Caution ; Throughout the procedure, great care must be taken

to avoid contamination.

Frequency of sampling

Where possible, samples should be taken daily from ships in transit.

From permanent stations, including Ocean Weather Ships, sampling should be

done on a bi-weekly basis.

Recommendations

Recognizing that the immediate surface might be more important with

respect to environmental processes, it is recommended that appropriate methods

will be developed to sample surface films.

Recognizing that suitable procedures to collect water samples for low

level hydrocarbon analyses from greater depths are not yet fully adequate, it

is recommended that suitable sampling devices and procedures be developed.

-'-or an appropriate amount of other suitable solvents; car should be exercised

in the use and handling of carbon tetrachloride.

2

hydrocarbon-free as determined by blanks

281
Sample Bottle with Cap Bottle Holder with Floatation Unit

Figure 1.

DISSOLVED HYDROCARBON SAMPLING DEVICE

Wlien taking a sample, the bottle cap is removed, the bottle is placed

in the holder by swinging open the stainless steel cage, and the

bottle is secured within the cage. The assembly is then thrown overboard from the bow, away from the ship but held by a retrieving line.

After the bottle sinks and the sample is obtained, the bottle is

hauled in, some water is spilled out of the bottle (to allow for

possible thermal expansion) , the. cap is fastened and the bottle is

labelled and stored away.

282
It is further recommended that methods be developed to collect samples

from ships other than research vessels without interfering with their normal

operations. For example, cartridges containing suitable absorbents may be

placed in a by-pass to the sea water intake.

Sample Preservation

As carbon tetrachloride is an effective bacteriostat , further preservation

of the samples is not necessary.

Recording of Samples

A log must be maintained to identify the samples, noting the position,

date and time. Specified environmental data should also be given when possible.

The Workshop suggested some modifications to the forTnat(s) as given in the

Operational Plan for the Pilot Project and recommended that the Joint Task

Team refine the reporting forms and include these incorporations in the final

version of the Operational Plan for the Pilot Project.

A label should be attached to the sample bottle bearing the sample

number from the log and the position, date and time of the sample. This was

to be designed by the Task Team for inclusion in the Operational Plan for the

Pilot Proj ect.

Dispatch of Samples

Sample bottles, together with the logs, should be packed securely in the i transit case provided (to be determined natior-ally) and sent to the appropriate

analysis laboratory.

Analysis Procedure

The Workshop decided to focus the quantitative analyses on aromatic

hydrocarbons because:

(1) They are considered to have the greatest environmental impact in

terms of toxicity;

(2) They seem to offer a means to differentiate between biogenic and

petroleum derived hydrocarbons;

(3) Relatively straightforward and sensitive analytical methods exist

for their estimation.

It is recommended, therefore, to use fluorescence spectrophotometry for

quantitative measurements as described below:

Processing and analysis of samples

After shaking the water~CCl^ mixture , allow the two phases to separate

,

ipet off the CCl^^ and place it in a clean glass bottle.

Caution must be exercised in the use and handling of CCL^.

283
Add 50 ml hydrocarbon-free CCl^ to the seawater, carry out a second

extraction and add CCI4 to the previous 50 ml. Measure the volume of sea- water processed.

Evaporate CCl^ in a rotary evaporator or with mild heating on a hot plate

(do not boil)

.

Prepare quantitative extract in n-hexane (5 ml clean volumetric flask)

.

Transfer to a 1 cm silica cell for fluorescence spectrophotometry.

Scan both excitation and fluorescence spectra. (Crude and residual fuel

oils have excitation and fluorescence maxima in the neighborhood of 310 and

360 nanometer, respectively. The optimum wavelength for excitation and

emission should be selected.)

The intensity of the fluorescence is measured and compared with a series

of standard solutions of similar composition and concentration under

identical instrumental conditions.

Finally, calculate the concentration of oil present in water.

Ref ; E. M. Levy, Water Research, 5^, 723 (1971)

Alternative Methods

UV-absorption spectrophotometric measurement after column chromatographic

clean-up and concentration (A. Zsolnay, Chemosphere , 6^, 253-260, 1973).

Other analytical methods such as gas chromatography are not meant to be

excluded. Indeed, gas chromatography provides much more information on the

composition of samples, but it is not sufficiently sensitive for the

concentrations expected to be encountered in other than highly polluted sea

areas

.

It is recommended that research be undertaken to develop and/or assess

simple, fast, reliable and inexpensive methods for future stages of the Pilot

Proj ect.

Handling of Data

Data obtained from the analysis of water samples should be recorded on

forms as developed by the Task Team for inclusion in the Operational Plan and

the forms submitted through national channels as established by the National

Coordinator, to the IGOSS "Responsible National Oceanographic Data Centers"

(RNODC's). The WC lODE's ad hoc Group on IGOSS Data Archiving and Exchange,

in conjunction with the ad hoc Group on Marine Pollution Data and the ad hoc

Group on Format Development, should be instructed to prepare a supplement to

the IGOSS Manual on Data Archiving and Exchange, outlining marine pollution

data archival arrangements.

^ API Reference crude oil (medium aromatic content) is recommended as standard.

284
STANDARDS AND INTERCOMPARISON CRITERIA

Co-Chairmen: Drs. J. NcNesby and

R. Hiltabrand

Rapporteurs: Dr. R. Pierce and

Ms. S. Dyszel

This session indicated the feasibility of the use of reference petroleum

samples; however, there is little, if any, information available on a standard

petroleum reference material for marine environmental monitoring.

In order for any material to qualify as a reference material, the

accuracy must be established by procedures such as those used for certification

of standard reference materials by the U.S. National Bureau of Standards.

These procedures may be obtained from the following reference:

"Standard Reference Materials: The Role of SRM's in Measurement

Systems by Cali, J.P. , et al, NBS Special Publication 260-46

(in press), Gaithersburg , Maryland, USA."

A complete evaluation of the analytical method used must accompany the

standard reference material before its reliability can be determined.

It is recommended, at this time, that (1) the American Petroleum Institute

(API) reference samples be used as standard reference material; however, it is

advisable that these samples undergo internal calibration by various

laboratories as soon as possible and that this calibration be supervised by a central coordinating agency such as the U.S. National Bureau of Standards to

establish the validity of the testing and the samples (these API samples can

now be obtained through Dr. J. R. Gould, Secretary, American Petroleum

Institute, 1801 K Street, N.W. , Washington, D.C. 20006); (2) future research

should investigate the "feasibility" of establishing other hydrocarbon

standard material in:

(the recommendations for specific standards in other materials depends upon

the specific analytical procedures applied) ; (3) all reporting methods should

be standardized; (4) the Systeme International d Unites (SI units) be used;

(5) all intercomparisons should include reporting blanks with each set of

analyses; and (6) multiple samples should be obtained from each sample site

and analyzed when possible.

(a)

(b)

(c)

seawater

sediments

biological material

285

OIL IN MARINE ORGANISMS AND SEDIMENTS;

SAMPLING AND ANALYTICAL METHODS

Co-Chairmen: Drs. F. Weiss and

J. Farrington

Rapporteur : Mr. R. Clark

General Comments on the Operational Plan

(1) The sampling and analysis of marine organisms and sediments are beyond the scope of the Pilot Project on Marine Pollution Monitoring under

the framework of IGOSS.

Justification ; This recommendation is made after consideration of

the current state-of-the-art of analytical methods and data interpretation

based on a broad evaluation of numerous scientific papers including the

summaries of presentations at this symposium.

(2) However, we believe there are several suggestions that can be set

forth for establishing future priorities for the use of marine organisms and

sediments in petroleum pollution monitoring.

Recommendations

(1) Sampling

(a) We recommend the development of acceptable sampling methods.

The sampling methods should be based on consultations between biologists,

geologists, analytical chemists and geochemists. In order to avoid contamination

of the samples, procedures such as those described by Grice, et al, (1972)

should be used.

Ref: Grice, G. D. Harvey, G. R. ,Bowen, V. T. and

Bacus, R. H. , The Collection and Preservation of

Open Ocean Marine Organisms for Pollutant Analysis,

Bull . Envir. Contam . Toxicol . 7, 125-132 (1972).

(b) Once acceptable sampling methods have been developed, these

methods should be employed wherever possible, to collect, sort, catalogue,

preserve, and archive marine organism and sediment samples for future chemical

analysis. Samples must be accompanied by adequate documentation.

(c) The development or choice of a suitable archiving program for

biological and sediment samples can only be initiated after consultation with

experts in this field, such as those of the Smithsonian Institution.

\ 287
(2) Analysis

(a) The current methods of analysis for petroleum in marine

organisms and sediments are still in a research mode with respect to

applicability in an international monitoring program. This is especially

apparent when cons'idering monitoring in those areas where organisms and

sediments may be expected to have low concentration levels, that is, on the

order of 10"^ grams of petroleum per gram dry weight of sample.

(b) The presentations at this symposium as described in the summaries

of papers contain many promising methods of analysis currently underway as part of national research programs. This research should be encouraged and

the exchange of information and ideas should be channeled through IGOSS.

(c) Once methods applicable to monitoring programs have been

developed, they may then be applied to the archived samples and to future

sample collections.

Analytical Standards and Criteria

Refer to report on Standards and Intercomparison Criteria and the section

below on Supporting Studies for Expansion and Further Development of the

Pilot Project.

Data Handling

To be determined by future Workshops at such time as sampling for

petroleum in sediments and marine organisms becomes a part of the Pilot

Project. In the interim, data from research data will be reported and

exchanged under the chemistry format as developed by the IOC WC for lODE.

Contents of Final Report on Pilot Project

With regard to one specific suggestion in the Joint lOC/WMO Planning Group

for IGOSS document of October 1973 (IOC-WMO/IPLAJSI-II/3) on page 32 of Annex V,

section b, item 8, concerning analysis of pollutants in fish meal and fish

solubles, we would recommend that the analysis for petroleum not be considered

during the Pilot Project. The analytical methods are not to a sufficient

degree of standardization to permit a global monitoring of the world fish

meal industries. In addition, low level petroleum contamination may be

introduced during the processing of the fish meal. Thus, analysis would not

provide a true assessment of natural conditions.

Supporting Studies for Expansion and Further Development of the Pilot Project

We would recommend that consideration be given to the convening of a future scientific workshop solely on the sampling and analysis of marine

organisms and sediments and that this workshop be called in January 1976 to assess the state-of-the-art. If sufficient national or regional efforts have

provided acceptable methods for sampling, analysis and data interpretation, a period of one year following this workshop should be provided for an intercalibration of methods between participating national centers under the

288
designation of IGOSS. An evaluation of the sampling and analytical methods

for petroleum in marine organisms and sediment should be presented at the end

of the Pilot Project.

Should the opportunity arise, organisms collected during surface tar ball

sampling tows (neuston net) should be separated from the tar balls and debris

and preserved for future analysis. A complete description of the net tow

sample must be included with the biological sample. Only excised tissue

samples and organ samples should be analyzed when methods applicable to the

monitoring program are developed since the exterior of the organisms will

probably be subjected to contamination by petroleum in the neuston tows.

Technical Assistance Program Needs

Specific training and education programs in the areas of chemical

oceanography, organic analytical chemistry and routine laboratory instrumentation

and electronics should be encouraged in context of IGOSS , especially through

some of the existing international development programs. We would recommend

two levels of effort:

(1) A technical training program of 2-3 month duration to provide a practical training session for field and laboratory technicians at an existing

petrolevim pollution monitoring laboratory, such as the Bermuda Biological

Station for Research. The first aspects of these training sessions should be

initiated no later than six months after the start of the Pilot Project.

(2) Exchange of field and laboratory-level working scientists

between existing petroleum pollution monitoring laboratories and those

national research centers wishing to develop a capability for such monitoring

efforts. The duration of each exchange would vary with the individual

scientist but would probably be for a period of two months to 4 years. This

program should be initiated immediately after the start of the Pilot Project.

289
/ s
ASSESSMENT OF BIOLOGICAL EFFECTS OF PETROLEUM HYDROCARBON POLLUTION

Chairman: Mr. M. Stansby

Rapporteur: Dr. T. Joyner

Methodology

This session dealt with matters which are not directly concerned with

monitoring, per se . The monitoring will not in any case deal directly with

biological assessments, so we are not commenting on biological assessment

methods. We feel, however, that the methods to be used in the Pilot Project

and in subsequent extensions of such work should receive input from this

session to indicate types of monitoring information which would be most useful to research attempting to evaluate effects of petroleum hydrocarbons

upon the biota. This topic was considered in the paper by Dr. La Roche and

it made up a large part of the discussion following the paper in this session.

It was also discussed in Mr. Stansby 's paper during the final session on May 15: Biological Environmental Effects.

During discussions at another session, the possibility was brought up of

sampling surface water films during the forthcoming Pilot Project. The

taking of such samples would be extremely advantageous for research worker's

information. It is realized that it would probably be impractical to adopt

such sampling routinely, for the upcoming Pilot Project. It is recommended,

however, that if even a small part of the samples could be taken in this way,

this should be considered. Even should this be impossible, we strongly

recommend that ways to do this be considered for future projects. We know

that devices have been used in the past for collecting thin films at the

surface in the open ocean. A device employing a rotating cylinder mounted

in a wood frame which allowed it to be operated in somewhat rough seas, was built and used at Scripps Institution of Oceanography, a few years ago.

Since the primary concern about oil pollution in the ocean is its impact

on living resources and human health, means for monitoring the effects of

petroleum oils on these resources and their products that are used as items

of human diet must be developed. These should include the selection of

appropriate marine organisms, collecting, preserving, shipping and processing

of samples as well as the development of appropriate analytical techniques.

For the selection and sampling of appropriate marine organisms, it is

suggested that particular attention be paid to the sea-atmosphere and sea- sediment interfaces where, because of the natural concentration of initially

dispersed pollutants on these surfaces, the greatest contamination of

organisms can be expected to occur. Examples would be the contamination of

the eggs and larvae of pelagic fish and zooplankton and of unicellular marine

plants at the sea-air interface by thin films of oily pollutants , and the

contamination of the benthic fauna that form the basic food of bottom fish by

oily pollutants absorbed onto settling particles.

Supporting Studies for Expansion and Further Development of the Pilot Project

Responding to the request of the lOC/WMO Task Team on the Marine Pollution

Monitoring Pilot Project (8-10 May, 1974) that the Workshop consider such

291
methods of marine pollution monitoring as analysis of pollutants in fish meal

from the world fish meal industries, we recommend that the participating States,

in their national marine research programs, be encouraged to undertake development of appropriate methods for sampling and analyzing fish, destined for the

production of fish meal, for components of petroleum oils that could adversely

affect the palatability or safety as foodstuffs of fish meal products. As

these methods are developed and standardized, they could be considered for

future inclusion in an expanded pollution monitoring program.

We recommend that research be pursued toward developing methods for

sampling marine organisms, especially fin fish, in such a way that subsequent

analysis of the resulting sample would give hydrocarbon values predictive of

potential harm to the fish. This could probably be achieved by finding parts

(organs or tissues) of the fish where the hydrocarbons were present in such

a way that they either were in a position in close proximity to vulnerable

sites within the fish or could be readily mobilized into such position.

Present practice of analyzing whole fish results in including hydrocarbons

often detoxified in fatty areas or sometimes even the inclusion of hydrocarbons

in feed in the digestive tract which would never or only partially be laid

down in the tissue of the fish.

Biological Indicators and Accumulators for Marine Pollution Monitoring

(Surveillance)

The report of the Third Session of the IOC Group of Experts on Oceanographic

Research as it relates to IGOSS was reviewed where reference is made to the use of biological indicators and accumulators as a means for marine pollution

monitoring; (Document SC-IOC/IRES-IIl/3 , Annex IV refers.)

The term "bioassay" as used in paragraph 2 of Item 7 of the Report is

open to conflicting interpretations. If used in the sense of using biological

organisms to indicate the effects of pollution oij the life processes of the

organism (as in the case of laboratory mice) , then we do not believe that it

could be effectively applied to pollution monitoring on a global scale. The

range of interfering effects on the organism from environmental parameters

other than those being monitored would be too great to permit precise

interpretation of observed effects.

If used in the sense of indicating the presence or absence of a pollutant

by its physical accumulation on the organism, then the selection and testing

of the suitability of organisms adequate to specific geographic areas of

interest to the Pilot Project should be encouraged by the participating Member

States. When such bioassay systems are sufficiently developed they can be

proposed by the member states for inclusion in the Pilot Project.

Technical Assistance Program Needs

Use should be made of national laboratories possessing expertise in

monitoring and other analytical procedures including biological assessment.

When program needs require assistance in any of these fields it should be

possible to arrange for trainees to be stationed for limited periods of time

at such laboratories to enable them to acquire experience in the technique

desired. For example, there are several laboratories in the United States,

292
especially on the Pacific Coast, experienced in biological assessment

techniques involving petroleum oil which could assist in such work for a limited number of trainees.

293

WORKSHOP CONCLUSIONS AND RECOMMENDATIONS ON DATA HANDLING

Co-Chalrmen: Mr. R. Morse and Mr. T. Winter feld

Data Handling

The Workshop recognizes the importance of making data and information

resulting from the pollution monitoring programs routinely available on an international basis.

The Workshop reaffirms the previous recommendations of planners of IGOSSaf filiated projects that, on the subjects of data (recording data formats,

data exchange and archival mechanisms and procedures , inventories and data

documentation) , specific advice and guidance would be sought from the IOC WC

on International Oceanographic Data Exchange (lODE)

Forms for visual observations of oil slicks and other floating pollutants,

and for sampling and reporting of particulate petroleum residues , and for the

results of analyses of dissolved/dispersed oil, should be submitted through

national channels, as already established under the WC lODE (in accordance

with procedures to be included in the IOC Manual on IGOSS Data Archiving and

Exchange) , to the IGOSS "Responsible National Oceanographic Data Centers"

(RNODC's).

Recommendations

(1) All participants in the Pilot Project should be made aware of and

urged to complete and submit, in timely fashion, the IOC first-level

inventory, ROSCOP (Report of Observations /Samples Collected by Oceanographic

Programs)

(2) The WC lODE's ad hoc Group on Marine Pollution Data Exchange, in

collaboration with the ad hoc Group on IGOSS Data Archiving and Exchange and

the ad hoc Group on Format Development, is requested to review the data

formats and procedures of IPLAN-II as modified by this Workshop, and develop

appropriate guidelines for the reporting, inventorying, documenting and

international exchange of marine pollution data as a supplement to the IGOSS

Manual on Data Archiving and Exchange.

(3) The WC lODE's ad hoc Group on Marine Pollution Data Exchange should

accelerate its efforts to develop inventory and documentation procedures for

marine pollution data and place priority in this development upon petroleum

hydrocarbon data, so as to minimize the variability of local or national

reporting formats in use at the commencement of the Pilot Project.

(4) All marine pollution (chemistry) data and information, whether or not

suitable for centralized archiving and routine exchange, should be inventoried

and fully documented (see Annex I) and incorporated into a centralized

international referral system as is being developed by the lODE ad hoc Group

on Marine Pollution Data Exchange and the Joint Task Team (IOC, ICES, IAEA,

FAO, IHO, WMO, WHO, IMCO, UNEP) on Interdisciplinary and Interorganizational

Data and Information Management and Referral (IMAR)

295
(5) Any samples obtained under this Pilot Project, which are to be

stored for future chemical analysis should be accompanied by documentation at

the same level of detail as is being prescribed for actual data and inventories

of data (see 3 and 4 above)

296
Annex I Recommendations on Data Handling

Minimum General Documentation to Accompany Marine

Chemical, Biochemical and Geochemlcal Data and Inventories

(NOTE; This documentation Is to supplement that required)

(by the basic Data Documentation Form (DDF) which pro- ) (vldes for time, position, cruise number, name of Instltu-)

(tlon and scientist, related meteorological data, etc. )

Sampling Documentation

Salinity

Temperature

Bottom Depth

Sampling Apparatus

Filtered/Unfiltered

Filter Specs.

Hydro Cable (Type,

Condition, Greased?)

Species

Sex

Weight

Length

Dissection Procedure

Tissue

% Moisture

% Organic Matter

Size Fraction

Mineralogy

Water

X

X

X

X

X

X

T,0

Biological

X

X

X

X

Sediment

T,0

X

X

X

X

X

X

X

X

X

X

X

X

297
Water Biological Sed iment

Depth in Core X

Type Container

Reagents Added

Storage (Frozen, etc.)

Length of Storage

Storage Documentation

Water Biological

X X

X X

X X

X X

Sediment

X

X

X

X

Sample Split

Extraction Procedure

Concentration Procedure

Digestion Technique

Sample Purification

Lab Sample ID No.

Sample Preparation Documentation

X X

X X

X X

X

X X

X X

X

X

X

X

X

X

Analysis Documentation

Date of Analysis

Analytical Method*

Make & Type of Instrument

X

X

Number & Concentration Range X

of Calibration Standards

Blank Value

Precision

Estimated Accuracy

Basis of Rept. Data

(Wet, Dry, etc.)

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

298
Water Biological Sediment

Units

No. of

of

Replicate

Measurement

Analyses

XXXXX

X

Confirmation by Other P P P

Technique

PCB Analysis - Yes /No? P P P

(in Conjunction with DDT)

Legend

P = Pesticides

T = Trace Elements

X = All Samples

0 = Organics

*Each specific analytical technique requires additional documentation related

to that technique; i.e., gas chromatography, mass spectroscopy, UV

flourescence, neutron activation analysis, etc. ATTACH SEPARATE SHEET.

299

LIST OF PARTICIPANTS IN WORKSHOP

Mr. P. Agafonov

Mr. M. C. Casquinho

Dr. S. N. Chesler

Mr. R. C. Clark, Jr.

Dr. J. C. Duinker

Ms. S. Dyszel

Dr. M. Ehrhardt

Dr. J. W. Farrington

Mr. M. Gruenfeld

Dr. H. S. Hertz

Oceanographic Committee of the USSR

11, Gorky Street

Moscow

USSR

Navy Department

Ministerio da Marina

Lisbon

PORTUGAL

Analytical Chemistry Division

National Bureau of Standards

Washington, D.C. 20234

USA

Northwest Fisheries Center

National Marine Fisheries Service

2725 Montlake Blvd., East

Seattle, Washington 98112

USA

Netherlands Institute for Sea Research

P.O. Box 5g, Den Burg

NETHERLANDS

Analytical Chemistry Division

National Bureau of Standards

Washington, D.C. 20234

USA

Institut fiir Meereskunde an der

Universtat Kiel

23 Kiel, Diisternbrooker Weg 20

FRG

Chemistry Department

Woods Hole Oceanographic Institute

Woods Hole, MA 02543

USA

Environmental Protection Agency

Industrial Waste Treatment Laboratory

Edison, New Jersey 08817

USA

Analytical Chemistry Division

National Bureau of Standards

Washington, D.C. 20234

USA

301
Dr. R. R. Hiltabrand U.S. Coast Guard

Avery Point R&D Center

Groton, CT 06340

USA

Mr. S. Hori Oceanographic Division

Hydrographic Department

Maritime Safety Agency

5-Chome, Tsukiji, Chuo-ku, Tokyo 104

JAPAN

Mr. K. H. Hughes National Oceanic and Atmospheric

Administration

Bldg. 5, Room 805

6010 Executive Blvd.

Rockville, Maryland 20852

USA

Mr. R. C. Junghans National Oceanic and Atmospheric

Administration

Bldg. 5, Room 805

6010 Executive Blvd.

Rockville, Maryland 20852

USA

Mr. F. K. Kawahara Environmental Protection Agency

NERC, MDQARL

1014 Broadway

Cincinnati, Ohio 45202

USA

Dr. D. P. Kohnke Deutsches Oceanographisches Datenzentrum

Bernhard-Nacht-Str. 78

D-2000 Hamburg 4

FRG

Mr. R. C. Landis National Oceanic and Atmospheric

Administration

Bldg. 5, Room 805

6010 Executive Blvd.

Rockville, Maryland 20852

USA

Dr. E. M. Levy Bedford Institute of Oceanography

P.O. Box 1006

Dartmouth, N.S.

CANADA

Mr. W. E. May Analytical Chemistry Division

National Bureau of Standards

Washington, D.C. 20234

USA

302
Mr. W. N. Mbote

Dr. J. R. McNesby

Mr. R. E. Morris

Mr. R. M. Morse

Mr. J. C. Mourlon

Mr. H. Mujica

Dr. P. W. Nasmyth

Mr. T. Orekoya

Dr. R. H. Pierce

Mr. J. Ros

Ministry of Tourism and Wildlife

P.O. Box 4024

KENYA

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

USA

East African Marine Fisheries

Research Organization

P.O. Box 668 27-02

ZANZIBAR

Environmental Data Service

National Oceanic and Atmospheric

Administration

Washington, D.C. 20235

USA

Centre National pour L* Exploitation

des Oceans

39, Avenue d'lena

Boite Postale 107

75016 Paris

FRANCE

Comislon Nacional de Oceanografia

Capce Sayandi 430 Piso 20

Montevideo

URUGUAY

Ocean Physics Division

Marine Sciences Directorate

Department of the Environment

5th Floor, 1230 Governmental Street

Victoria, B.C.

CANADA

Federal Department of Fisheries

P.M.B. 12529, Lagos

NIGERIA

University of Rhode Island

Plant Pathology-Enthomology

Kingston, Rhode Island 02881

USA

Institute Espanol de Oceanografia

Box 22

San Pedro del Pinatar

SPAIN
Dr. A. I. Simonov

Mr. M. E. Stansby

Mr. B. J. Thompson

Mr. T. H. Thompson

Dr. F. T. Weiss

Mr. T. Winterfeld

Mr. R. M. Wright

Mr. R. A. Zachariason

Dr. A. Zsolnay

State Oceanographic Institute

6 Kropotkinsly Pereulok

Moscow G-34

USSR

National Marine Fisheries Service

Northwest Fisheries Center

2725 Montlake Blvd.

Seattle, Washington 98112

USA

NOAA/NWS (W6)

2807 Botany Lane

Bowie, Maryland 20715

USA

Swedish Meteorological and Hydrological

Institute

P.O. Box 12108

70223 Stockholm

SWEDEN

Shell Development Company

P.O. Box 481

Houston, Texas 77001

USA

Environmental Data Service

National Oceanic and Atmospheric

Administration

Washington, D.C. 20235

USA

Mines and Geology Division

P.O. Box 181, Kingston 6,

Jamaica

WEST INDIES

National Oceanic and Atmospheric

Administration

Bldg. 5, Room 805

6010 Executive Blvd.

Rockville, Maryland 20852

USA

Bermuda Biological Station

St. George's West

BERMUDA

304
Dr. T. Joyner National Marine Fisheries Service

Northwest Fisheries Center

2725 Montlake Blvd.

Seattle, Washington 98112

USA

Represented

:

Food and Agriculture Organization

Via delle Teme dl Caracalla

00100 Rome

ITALY

Mr. B. Okamura Inter-Governmental Maritime Consultative

Organization

101-104 Piccadilly

London

UK

Dr. I. Zrajevsklj Ocean Affairs Branch

Marine and Aeronautical Division

World Meteorological Organization

Case Postale No 5, Geneva 20

CH-1211

SWITZERLAND

Dr. A. Tolkachev Intergovernmental Oceanographlc Commission

UNESCO

Place de Fontenoy

75700 Paris

FRANCE

Dr. M. Ohwada Intergovernmental Oceanographlc Commission

UNESCO

Place de Fontenoy

75700 Paris

FRANCE

305
V
MARINE POLLUTION MONITORING (PETROLEUM) SYMPOSIUM AND WORKSHOP

National Bureau of Standards

Gaithersburg , Maryland

May 13-17, 1974

Symposium Participants, Authors and Speakers

Donald D. Adams

Old Dominion University

Institute of Oceanography

Norfolk, VA 23508

Peter Agafonov

Oceanografic Committee of the USSR

1 1 , Gorky Street

Moscow

USSR

Mark Ahmadjian

University of Rhode Island

Chemistry Department

Kingston, RI 02881

A. M. Ahmed

Department of Chemical Engineering

Massachusetts Institute of Technology

Cambridge, MA 02139

W, T. R. Allen

Atmospheric Environment Service

4905 Dufferin Street

Downsview, Ontario, M3H 5T4

CANADA

Robert Alvarez

Office of Standard Reference Materials

National Bureau of Standards

Washington, DC 20234

Ernest Ambler

Office of the Director

National Bureau of Standards

Washington, DC 20234

Michael Anbar

Stanford Research Institute

333 Ravenswood Avenue

Menlo Park, CA 94025

Thomas S. Austin

Page Building No. 2 Washington, DC 20235

Charles C. Bates

U.S. Coast Guard

5S07 Massachusetts Avenue, NW Washington, DC 20016

Barbara M. Baum

Harvard University

40 Oxford Street

3rd Floor ESL

Cambridge, MA 02138

Edward R, Baylor

Marine Sciences Research Center

State University of New York

Stony Brook, NY 11790

Roger M, Bean

Battel 1 e-Northwest

P.O. Box 999

Richland, WA 99352

M. D. Beasley

Department of Chemical Engineering

Massachusetts Institute of Technology

Cambridge, MA 02139

Max Bechet

Regie des Voies aeriennes

AV. des Arts 41

B 1020 Bruxelles

BELGIUM

Donald A. Becker

Activation Analysis Section

National Bureau of Standards

Washington, DC 20234

Michael E. Bender

Virginia Institute of Marine Science

Gloucester Point, VA 23062

RADM W. M. Benkert

U.S. Coast Guard

Washington, DC 20590

W. D. Bennett

Canadian Embassy

1746 Massachusetts Avenue, NW Washington, DC 20036

Pete Benville, Jr. National Marine Fishery Service

P.O. Box 98 Tiburon, CA 94920

Michael W. Beug

The Evergreen State College

Olympia, WA 98505

Rudolf H. Bieri

Virginia Institute of Marine Science

Gloucester Point, VA 23062

Jaspar Bilal

Indonesian Petroleum Institute

Lemigas, Jakarta

INDONESIA

J. W. Blaylock

Battel 1 e-Northwest

P.O. Box 999

Richland, WA 99352

Daniel Bottom

University of Delaware

Department of Geology

Newark, DE 19711

307
Gerald W. Bowes Space Sciences Laboratory

University of California

Berkeley, CA 94720

Ruby N. Boyd

Physical Chemistry Division

National Bureau of Standards

Washington, DC 20234

J. M. Brooks

Department of Oceanography

Texas A&M University

College Station, TX 77840

C. W. Brown

Department of Chemistry

University of Rhode Island

Kingston, RI 02881

Dail W. Brown

NCAA

6010 Executive Blvd.

Rockville, MD 20852

Ralph A. Brown

Esso Research & Engineering Company

P.O. Box 121 Linden, NJ 07036

H. E. Bruce

National Marine Fisheries Service

Auke Bay, AK 99821

Thomas E. Burke

Bureau of Land Management

Department of Interior

Division of Marine Minerals

Washington, DC 20240

M. D. Burkhart

8401 Echo Lane

Clinton, MD 20735

K. Burns

Woods Hole Oceanographi c Institute

Woods Hole, MA 02543

James N. Butler

Harvard University

Pierce Hall

29 Oxford Street

Cambridge, MA 02138

John A. Calder

Florida State University

Department of Oceanography

Tallahassee, FL 32306

N. J. Campbell

Marine Sciences Directorate

Department of the Environment

615 Booth Street

Ottawa, Ontario

CANADA

D. C. Canada

Union Carbide

P.O. Box Y, Bldg. 9735

Oak Ridge, TN 37830

Thomas Carver

N0AA-NMFS-F18

Washington, DC 20235

H. F. Casey

Maritime Administration

Washington, DC 20230

Manuel C. Casquinho

Navy Department

Ministerio da Marlnha

Li sbon

PORTUGAL

D. E. Cawlfied

Pacific Northwest Environmental

Research Laboratory

Environmental Protection Agency

Corvallis, OR 97330

William J. Chang

U.S. Coast Guard

Department of Transportation

Avery Point

Groton, CT 06340

Walter B. Chappel

Maritime Administration

Environmental Activities Group

14th & E Streets, NW CODE M730.2

Washington, DC 20230

Stephen N. Chesler

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234

James M. Cimato

Todd Research & Technical

P.O. Box 1600

Galveston, TX 77550

Robert C. Clark, Jr. Northwest Fisheries Center

National Marine Fisheries Center

2725 Montalke Blvd. East

Seattle, WA 98112

J. B. Colton

National Marine Fisheries Service

Washington, DC 20235

T. J. Conomos

U.S. Geological Survey

Menlo Park, CA 94025

Geraldine V, Cox

Raytheon

Box 360

Portsmouth, RI 02871

Stuart P. Cram

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234

308
Walter J. Cretney

Ocean Chemistry Division

Department of the Environment

211 Harbour Road

Victoria, British Columbia,

CANADA

Frank B. Cruickshank

Atlantic Richfield Company

3144 Passyunk Avenue

Philadelphia, PA 19145

Morton Curtis

U.S. Coast Guard

Research Development Center

Avery Point

Groton, CT 06340

Millard L. Cutler

NOAA

National Ocean Survey (C52)

6001 Executive Blvd., WSC #1, Rm. 910

Rockville, MD 20852

George T. Dagg

Maritime Administration

Department of Commerce

Washington, DC 20230

D. M. Damkaer

NOAA-ERL

University of Washington WB-10

Seattle, WA 98195

Roger Dille

TEXACO

P.O. Box 3407

Richmond, VA 23234

Louis H. DiSalvo

Naval Biomedical Research Laboratory

Naval Supply Center

Oakland, CA 94625

K. Donaldson

BP North America Incorporated

620 5th Avenue

New York, NY 10020

D. J. Donovan

Department 6f Chemistry

Dowdoin College

Brunswick, ME 04011

R. C. Dow

Marine Department of Marine Resources

Augusta, ME 04330

R. L. Dryfoos

National Marine Fisheries Service

Washington, DC 20235

Jan C. Duinker

Netherlands Institute for Sea Research

P.O. Box 5g Den Burg

NETHERLANDS

Nishan Dulgerian

Wheeler Industries, Incorporated

1028 Connecticut Avenue, NW Washington, DC 20036

T. K. Duncan

Virginia Institute of Marine Science

Gloucester Point, VA 23062

S. N. Dwivedi

National Institute of Oceanography

Cavanxalam P.O. GOA

INDIA

Susan Dyszel

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234

A. C. Efromson

Department of Chemical Engineering

Massachusetts Institute of Technology

Cambridge, MA 02139

Manfred Ehrhardt

Institut fur Meereskunde an der

Universitat Kiel

23 Kiel, Dusternbrooker Weg 20

FEDERAL REPUBLIC OF GERMANY

J. J. Elliott

ESSO Research & Engineering Company

Linden, NJ 07036

Delmo P. Enagonio

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234

Robert J . Farl and

National Oceanographi

c

Instrumentation Center

NOAA-NOS-NOIC

Rockville, MD 20852 (WNYA)

John W. Farrington

Chemistry Department

Woods Hole Oceanographi c Institute

Woods Hole, MA 02543

Milton H. Feldman

National Environmental Research Center

Office of Research & Development

U.S. Environmental Protection Agency

Corvallis, OR 97330

E. P. Ferrero

U.S. Department of Interior

Bureau of Mines

P.O. Box 1398

Bartlesvil le, OK 74003

Carl W. Fisher

Oceanographic Division

National Ocean Survey

Washington Science Center, Bldg. 1 Rockville, MD 20852

Frank R. Fisher

Alyeska Pipeline Service Company

1815 South Bragaw

Anchorage, AK 99504

Donald G. Fletcher

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

309
Dennis G. Ford

Bechtel Corporation

Environmental Services Department

P.O. Box 2277

Gaithersburg, MD 20760

Donald C. Ford

Atlantic Richfield Company

400 E. Sibley Blvd.

Harvey, IL 60426

Nancy Foster

Department of Interior

U.S. Fish and Wild Life Service

1044 West Side

Gaithersburg, MD 20760

Peter H. Freeman

Smithsonian Institution

Washington, DC 20560

Lois Frolen

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

Sidney R. Galler

Department of Commerce

Washington, DC 20234

William D. Garrett

Naval Research Laboratory

CODE 8330

Washington, DC 20375

Donald C. Gordon, Jr. Fisheries & Marine Service

Marine Ecology Laboratory

Bedford Institute of Oceanography

Dartmouth, Nova Scotia B2Y 4A2

CANADA

J. R. Gould

American Petroleum Institute

1801 K Street, NW Washington, DC 20006

Cary C. Gravatt

Office of Associate Director

for Programs

National Bureau of Standards

Washington, DC 20234

David R. Green

University of British Columbia

Ocean Chemistry, 211 Harbour Road

Victoria, British Columbia

CANADA

M. G. Gross

National Science Foundation

Washington, DC 20024

Michael Gruenfeld

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NBS-114A (REV. 7-73)

U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NBS Spec. Publ. 4092. Gov't Accession

No.

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

MARINE POLLUTION MONITORING (Petroleum)

Proceedings of a Symposivnn and Workshop held at the National

Bureau of Standards, Gaithersburg, Maryland, May 13-17, 1974

5. Publication Date December 1974

6. Performing Organization Code

7. AUTHOR(S)

R. C. Junghans , Conference Coordinator

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

^ DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

The Intergovernmental Oceanographic Commission (IOC)

The World Meterological Organization (WMO)

The U. S. Department of Coimnerce

13. Type of Report & Period Covered

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 74-31142

16. ABSTRACT (A 200-word or less factual summary of most si^ificant information. If document includes a significant

bibliography or literature survey, mention it here.)

These proceedings contain the invited plenary lectures representing

pertinent scientific, environmental, and regulatory aspects of petroleum

hydrocarbon measurements, the summaries of the contributed papers, dealing with specific scientific developments and recommendations, and the

recommendations of the topical discussion groups. Also included is a report of an international workshop which provides specific recommendations for the initiation of an coordinated Pilot Project for marine

pollution (petroleum) monitoring.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons) Analytical methods; data reporting procedures; Intergovernmental Oceanographic Commission (IOC); marine pollution (petroleum) monitoring;

Maritime Administration (MarAd) ; National Bureau of Standards (NBS); National Oceanic

and Atmospheric Administration (NOAA) ; petroleum hydrocarbon measurement ; oil slicks

and tar balls; sampling methods; World Meterological Organization (WMO).

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293

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