NOAA/University of Miami Joint Publication

NOAA Technical Memorandum NOS NCCOS 9

University of Miami RSMAS TR 2005-01

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**Coastal and Estuarine Data Archaeology and Rescue Program**

**1983**

**BISCAYNE BAY HYDROCARBON STUDY**

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**University of Miami**

**Rosenstiel School of Marine and Atmospheric Science**

February 2005 **Miami, FL**

**US Department of Commerce**

**National Oceanic and Atmospheric Administration**

**Silver Spring, MD**

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height="0.5138888888888888in"}

**Miami-Dade County**

**Department of Environmental Resources Management**

**Miami, FL**

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height="9.722222222222222e-2in"}

NOAA/University of Miami Joint Publication

NOAA Technical Memorandum NOS NCCOS 9

University of Miami RSMAS TR 2005-01

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height="9.722222222222222e-2in"}

**1983**

**BISCAYNE BAY HYDROCARBON STUDY**

> FINAL REPORT
>
> by
>
> Eugene F. Corcoran,
>
> Melvin S. Brown, Frederick R. Baddour, Steven A. Chasens
>
> and Ana D. Freay
>
> Rosenstiel School of Marine and Atmospheric Science
>
> University of Miami
>
> 4600 Rickenbacker Causeway
>
> Miami, FL 33149
>
> Project Officer
>
> J. Alan Huff, Senior Biologist
>
> Bureau of Marine Science and Technology
>
> Department of Natural Resources, State of Florida
>
> 100 Eight Avenue, S.E.
>
> St. Petersburg, FL 33701

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height="4.1666666666666664e-2in"}

A. Y. Cantillo

NOAA National Ocean Service

(Editor, 2005)

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height="1.2638888888888888in"}

February 2005

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United States National Oceanic and

Department of Commerce Atmospheric Administration National Ocean Service

Carlos M. Gutierrez Conrad C. Lautenbacher, Jr. Richard W. Spinrad

Secretary Vice-Admiral (Ret.), Assistant Administrator

Administrator

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height="9.722222222222222e-2in"}

For further information please call or write:

NOAA

National Ocean Service

National Centers for Coastal Ocean Science

1305 East West Hwy.

Silver Spring, MD 20910

301 713 3020

COVER PHOTO: Department of Environmental Resources Management,
Metro-Dade County

Disclaimer

This report has been reviewed by the National Ocean Service of the
National Oceanic and Atmospheric Administration (NOAA) and approved for
publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for their use by the United
States Government.

**TABLE OF CONTENTS**

LIST OF TABLES i

LIST OF FIGURES iii

PREFACE v

ABSTRACT vii

EXECUTIVE SUMMARY ix

Location of study area ix

Purpose ix

Results ix

1\. Introduction 1

1.1. Purpose 1

1.2. History of Study Area 1

1.2.1. Background Information 1

1.2.2. Geography 2

1.2.3. Climatic Conditions 3

1.2.4. Ecology 3

1.2.5. Economy 4

2\. Methods 4

2.1. Study Area Location 4

2.1.1. Sample Station Locations 5

2.1.2. Criteria for Station Selection 5

2.1.2.1. Previous Studies and Dade County Water Quality Monitoring
Stations 5

2.1.2.2. Oil Sensitivity Index 5

2.1.2.3. Sediment Type 11

2.1.2.4. Vegetation Type 11

2.1.2.5. Circulation 11

2.1.2.6. Supratidal and Intertidal Areas 12

2.1.2.7. Boating Facilities 12

2.1.2.8. Proposed Boating Facilities 12

2.1.2.9. Boating Departure Routes and Destinations 12

2.1.2.10. Preferred Anchorage 12

2.1.2.11. Dredging, Spoil, Erosional and Depositional Areas 12

2.1.2.12. Land Use 13

2.1.3. Collections 13

2.1.4. Quality Assurance 16

2.2. Sediment Grain Size Analysis 17

2.3. Organic and Carbonate Content Analysis 18

2.4. Hydrocarbon Analysis 19

2.4.1. Sediment 19

2.4.2. Tissue 20

2.4.3. Water 20

2.4.4. Gas Chromatographic Analysis 21

2.5. Radiocarbon Dating 22

2.6. Computer Mapping 22

3\. Intercalibration 23

4\. Results and Discussion 23

4.1. Grain Size Analysis 23

4.2. Organic and Carbonate Content 23

4.3. Radiocarbon Dating 43

4.4. GC-MS Analyses 43

4.5. Hydrocarbon analysis and Distribution 50

4.5. Summary 91

5\. Acknowledgments 93

6\. Literature cited 94

Appendix A. Station location and collection methodology for Year 01 99

Appendix B. Station location and collection methodology for Year 02 103

Appendix C. Literature review 105

Appendix D. Detailed summary of aliphatic (f1) hydrocarbon
determinations for Year 01 113

Appendix E. Detailed summary of aromatic (f2) hydrocarbon determinations
for Year 01 279

Appendix F. Detailed summary of aliphatic (f1) hydrocarbon
determinations for Year 02 351

Appendix G. Detailed summary of aromatic (f2) hydrocarbon determinations
for Year 02 447

.c1.LIST OF TABLES

1\. Criteria used in selecting the first year\'s sediment sampling
stations. 7

2\. Gas chromatograph operating conditions for the second year study. 22

3\. Summary of intercalibration samples for the two-year study. 24

4\. Aliphatic hydrocarbon characterization of interlaboratory sediment
samples collected during Year 02. All values are corrected for percent
recovery and expressed on a dry weight bases. 25

5\. Aromatic hydrocarbon characterization of interlaboratory sediment
samples collected during year 02. All values corrected for percent
recovery and expressed on a dry weight bases. 26

6\. Summary of surface sediment (0-5 cm depth) grain size analysis. All
values are percent dry weight. 30

7\. Summary of total organic matter and carbonate content of surface
sediments (0-5 cm depth). 37

8\. Summary information for 14C dated sediment. 46

9\. Aliphatic hydrocarbon characterization of 14C dated sediment
samples. All values are corrected for percent recovery and expressed on
a dry weight bases. 47

10\. Aromatic hydrocarbon characterization of 14C dated sediment
samples. Values are corrected for percent recovery and expressed on a
dry weight bases (µg/g). 48

11\. Summary of GC-MS characterization of PAH homologs. 49

12\. Criteria for distinguishing petrogenic from biogenic hydrocarbons.
52

13\. Aliphatic hydrocarbon characterization of surface sediments
collected during Year 01. All values are corrected for percent recovery
and are expressed on a dry weight basis. 53

14\. Aromatic hydrocarbon characterization of surface sediments
collected during Year 01. Values are corrected for percent recovery and
are expressed on a dry weight basis. 57

15\. Surface sediment containing petroleum hydrocarbons collected during
the first year of the study. 67

16\. Aliphatic hydrocarbon characterization of tissue samples collected
during Year 01. All values are corrected for percent recovery and
expressed on a dry weight bases. 69

17\. Aromatic hydrocarbon characterization of tissue samples collected
during Year 01. All values are corrected for percent recovery and
expressed on a dry weight basis. 70

18\. Aliphatic hydrocarbon characterization of water samples collected
during Year 02. All values are corrected for percent recovery. 72

19\. Aromatic hydrocarbon characterization for water samples collected
during Year 02. All values are corrected for percent. 74

20\. Aliphatic hydrocarbon characterization of sediment samples
collected during Year 02. All values are corrected for recovery and
expressed on a dry weight basis. 79

21\. Aromatic hydrocarbon characterization of sediment samples collected
during Year 02. All values corrected for percent recovery. 81

22\. Aliphatic hydrocarbon characterization of tissue samples collected
during Year 02. All values are corrected for percent recovery and
expressed on a dry weight bases. 88

23\. Aromatic hydrocarbon characterization of tissue samples collected
during Year 02. All values are corrected for percent recovery and
expressed on a dry weight bases. 89

24\. Summary of petroleum hydrocarbon concentrations in surface
sediments for different geographical areas. 92

.c1.LIST OF FIGURES

1\. Biscayne Bay study area and sampling station locations for the Year
01 study. 6

2\. Study area and sampling station locations for the Year 02 study
(MISSING IN ORIGINAL\].

3\. Flow diagram of sample collection and storage procedures. 14

4\. Chromatograms of aliphatic (f1) fraction. Interlaboratory
calibration - offshore sediment samples - University of Miami. 27

5\. Chromatograms of aliphatic (f1) fraction. Interlaboratory
calibration - offshore sediment samples - Mote Marine Laboratory. 28

6\. Chromatograms of aliphatic (f1) fraction. Interlaboratory
calibration - offshore sediment samples - Jacksonville University. a)
Jetties samples, b) Atlantic Beach sample, c) sample N6A. 29

7\. Histogram of percent gravel in surface sediments (0-5 cm). 34

8\. Histogram of percent sand in surface sediments (0-5 cm). 35

9\. Histogram of percent silt-clay in surface sediments (0-5 cm). 36

10\. Histogram of percent organic matter in surface sediments (0-5 cm).
41

11\. Histogram of percent carbonate material in surface sediments (0-5
cm). 42

12a. Profile description of cores used in 14C dating.

12b. Profile description of cores used in 14C dating.
\[RECONSTRUCTION\].

13\. Scattergram of total PAHs (f2) measured by GC vs. PAHs measured by
GC-MS. 54

14a. Distribution of aliphatic hydrocarbons (f1) in surface sediments of
Biscayne Bay. \[ORIGINAL\] 65

14b. Distribution of aliphatic hydrocarbons (f1) in surface sediments of
Biscayne Bay. \[RECONSTRUCTION. HIGH VALUES UPSTREAM IN THE MIAMI RIVER
ARE NOT SHOWN. LOCATION OF LAND MASSES RELATIVE TO HYDROCARBON
DISTRIBUTIONS NOT CLEAR IN ORIGINAL. 66

15a. Distribution of aromatic hydrocarbons (f2) in surface sediments of
Biscayne Bay. \[ORIGINAL\] 67

15b. Distribution of aromatic hydrocarbons (f2) in surface sediments of
Biscayne Bay. \[RECONSTRUCTION. HIGH VALUES UPSTREAM IN THE MIAMI RIVER
ARE NOT SHOWN. LOCATION OF LAND MASSES RELATIVE TO HYDROCARBON
DISTRIBUTIONS NOT CLEAR IN ORIGINAL.\] 68

16\. Scattergram of salinity vs. total hydrocarbons (aliphatic +
aromatic). 69

17\. Chromatograms of aliphatic (f1) fraction. Surface water samples
collected in the Miami River. a) sample #207, b) sample #208. 79

18\. Chromatograms of aliphatic (f1) fraction. Surface water samples
collected in Goulds Canal. 80

19\. Chromatograms of aliphatic (f1) fraction. Surface water sample #238
collected in Military Canal. 81

20\. Chromatograms of aliphatic (f1) fraction. Miami River sediment
sample #214. 86

21\. Chromatograms of aliphatic (f1) fraction. Miami River sediment
sample #218. 87

22\. Chromatograms of aliphatic (f1) fraction. Little River sediment
sample #225. 88

23\. Chromatograms of aliphatic (f1) fraction. Goulds Canal sediment
sample #232. 89

24\. Chromatograms of aliphatic (f1) fraction. Military Canal sediment
sample #240. a) 0-5 cm depth, b) 60-65 cm depth, c) 120-125 cm. 90

25\. Chromatograms of aliphatic (f1) fraction. Flat tree oyster
collected from marina. 93

.c1.PREFACE

This final report is the culmination of a two-year project designed to
establish background levels of hydrocarbons to support oil spill impact
assessment and determine possible sources of petroleum contamination in
Biscayne Bay. The first year of the study supplied information on the
distribution of hydrocarbons in the surface sediments and selected
biota. The second year study used the previously developed database to
select areas which indicated petroleum contamination. These areas were
further evaluated by collecting and analyzing additional surface and
subsurface sediments, biota and water.

This report contains all information collected during the two year
project period. The information contained in this final report
supersedes all other materials in previous quarterly and annual reports.

.c1.ABSTRACT

A two year, comprehensive, quantitative investigation was conducted to
analyze and identify the spatial distribution of petrogenic and biogenic
hydrocarbons in sediments, surface waters, fish and shellfish of
Biscayne Bay, Florida.

The goal for the first year of the project was to establish baseline
information to support oil spill impact assessment and clean-up. One
hundred fifty-five sediment and eleven biota samples were collected. The
areas sampled included the Miami River, Intracoastal Waterway, tidal
flats, access canals and environmentally sensitive shorelines.

The second year of the study centered on areas exhibiting petroleum
contamination. These areas included the Miami River, Little River,
Goulds Canal, Black Creek and Military Canal. Surface and subsurface
sediment, biota and surface water were collected.

Sample collection, analyses, and data handling for the two year project
were conducted so that all information was court-competent and
scientifically accurate. Chain of custody was maintained for all
samples.

Total hydrocarbon content of surface sediments ranged from below
detection limits to a high of 2663.44 pg/g. Several sample stations
contained petroleum contamination. The majority of biota samples
exhibited hydrocarbon concentrations and characteristics that indicated
little, if any, petroleum contamination. Surface water samples ranged
from 0.78 to 64.47 µg/L and several samples contained petroleum
hydrocarbons.

Our results indicate several areas of petroleum contamination. These
areas are characterized by industrial complexes, port facilities,
marinas, major boating routes and many of the major tributaries emptying
into Biscayne Bay.

.c1.EXECUTIVE SUMMARY

> .c2.Location of study area

Biscayne Bay is a large lagoonal system located along the southeast
coast of Florida. The Bay extends from 25° 58\' N to 25° 24\' N
latitude, covers approximately 573 km2, and is almost entirely contained
within Dade County. The Bay is unique in many ways. It offers a large,
year-round protected body of water, with a great diversity of natural
resources close to a major metropolitan area (Miami) and has retained to
a large degree, in its southern extremities, a character of undisturbed
tropical naturalness. The local economy is tourism based and dependent
on climate and esthetics. The Bay plays a very important role in the
economy by supplying esthetics and extensive recreational and commercial
activities. The Bay contains within its boundaries the largest port
(dollar value of imports and exports) in Florida and the Biscayne
National Park.

The south Florida area is dominated by major vessel traffic routes which
encompass both offshore corridors and the Intracoastal Waterway. During
the late seventies a US Coast Guard survey revealed that in excess of
one million tons of crude oil per day passed within 25 miles or less of
the southern Florida coastline. In addition, over three million tons of
cargo are shipped via the Intracoastal Waterway through Biscayne Bay.
Fuel oil leads all of the commodities shipped by this route in volume.

The planned exploration for offshore oil and its increased production in
the Gulf of Mexico, Caribbean Sea and Mexico, the continuous growth of
the Dade County economy and its rapid movement towards becoming a major
trade center has increased substantially the probability of collisions
and groundings resulting in oil spills and inputs of urban petroleum
compounds. The prospect of a major oil spill occurring in the southern
Florida/Biscayne Bay area is so prominent that during 1981-82 the South
Florida Regional Planning Council produced three documents to assist in
response and clean-up. These are the \"South Florida Oil Spill Response
Handbook\", \"The Sensitivity of Coastal Environments and Wildlife to
Spilled Oil in South Florida\" and the \"South Florida Oil Spill
Sensitivity Atlas.\"

.c2.Purpose

The purpose of the two-year study was to supply the State of Florida
Department of Natural Resources with a quantitative, court-competent
database of the distribution of petroleum and naturally occurring
hydrocarbons in the Biscayne Bay lagoonal system. This data will supply
the needed background information to support oil spill clean-up and
evaluation. The first year study was designed to provide information
about the spatial distribution of hydrocarbons in the surface sediments
and marine organisms of commercial and recreational value. These data
were to be used to establish the present background levels and
distribution of petroleum and naturally occurring hydrocarbons within
the Bay and to assess any future contamination. In the event of an oil
spill these data can supply the necessary information needed to
determine its present and potential damage. The goal of the second year
of the study was to investigate and further quantify those areas where
petroleum contamination was found and to determine its possible sources.
In addition to surface sediment, subsurface sediment, surface water and
marine organisms were analyzed to accomplish this goal.

.c2.Results

During the two year duration of the study, 205 surface sediments, 27
surface water samples and 21 marine organisms were collected and
analyzed for hydrocarbons. Sediment collection sites for the Year 01
study were selected by incorporating criteria relating to the physical,

chemical, and biological processes and man\'s historical, present and
future usage of the Bay. The second year study focused on areas where
high concentrations of petroleum contaminated sediment were detected.

The total hydrocarbon content in the surface sediments ranged from below
detection limits to 2663.4 µg/g, surface waters ranged from 0.8 to 64.5
µg/L and organism samples ranged from 0.3 to 600.8 µg/g. Only one
organism sample collected during the two year project showed any
petroleum contamination. These were flat tree oysters collected from a
marina. Several of the surface water samples collected showed
indications of petroleum contamination. These samples were always
associated with canal systems. The sample containing the highest
concentration was collected in the Miami River and the lowest came from
Black Creek. The sediments were the best indicator of contamination
since they are the ultimate sink for this pollutant. A review of the
hydrocarbon content and indices for the sediment collected during the
first year indicated that 52 samples showed characteristics of petroleum
contamination. These areas were associated with two main usage
patterns. 1) Areas associated with boats and ships, e.g. major
transportation routes, moorings, cargo handling, and construction and
maintenance. 2) Areas which receive runoff and other inputs from the
highly urbanized regions of Dade County.

Four major study areas which showed high concentrations of petroleum
hydrocarbons were investigated during the second year of the study.
These included the Little River, Miami River, Black Creek/Goulds Canal,
and Military Canal. Surface water, marine organisms and additional
sediment samples were collected from these areas to assist in further
characterizing the magnitude of pollution and determine its sources.

The Miami River sediment had the highest concentrations of hydrocarbons
detected during the two year project. The River falls under both usage
patterns referenced above. It is a major complex for handling cargo,
ship maintenance and repair and also receives runoff from the highly
urbanized downtown Miami area. In contrast to the Miami River would be
the Little River experiences only minimal boat traffic but receives high
inputs of runoff from urbanized Miami. This area also showed elevated
levels of hydrocarbons of petroleum origin. Military Canal, which for
all practical purposes receives no boat traffic, indicated elevated
concentrations of hydrocarbons. This canal, located in the southern
portion of Biscayne Bay, drains a major military establishment. The
Black Creek/Goulds Canal area is characterized by two canals which
converge before emptying into Biscayne Bay. During the Year 01 study,
the sediment sample collected at the intersection of the two canals
indicated petroleum contamination, after further investigation during
Year 02 it was determined that the majority of the contaminants were
coming from Goulds Canal. This canal receives the majority of the small
boat traffic and contains two marinas.

The information gathered during the two-year study has established a
baseline for the distribution of hydrocarbons in Biscayne Bay. This
database will be most useful in future studies and for establishing
levels of contamination from oil spills or other sources of petroleum
contaminants. It has also established a benchmark from which future
changes in the concentration and distribution of hydrocarbons can be
compared.

**1983 BISCAYNE BAY HYDROCARBON STUDY**

> Eugene F. Corcoran, Melvin S. Brown, Frederick R. Baddour,
>
> Steven A. Chasens, and Ana D. Freay
>
> Rosenstiel School of Marine and Atmospheric Science
>
> University of Miami
>
> 4600 Rickenbacker Causeway
>
> Miami, FL

.c1.1. Introduction

> .c2.1.1. Purpose

The purpose of this two-year study was to supply the State of Florida
Department of Natural Resources with a quantitative, court-competent
database of the distribution of petrogenic and biogenic hydrocarbons in
the Biscayne Bay lagoonal system. This data was to supply the needed
background information to support oil spill clean-up and evaluation. The
first year study provided information about the spatial distribution of
hydrocarbons in the surface sediments. In addition selected biota of
commercial and recreational value were collected and analyzed. These
data were used to establish the present background levels and
distribution of petrogenic hydrocarbons within the Bay and can be used
to assess future contamination. In the event of an oil spill, these data
can supply the necessary information needed to determine its present and
potential damage. The goal of the second year of the study was to
investigate and further quantify those areas where petroleum
contamination was found during the first year study and to determine
their possible sources. Sediment, water and biota were collected and
analyzed using gas chromatography and gas chromatography /mass
spectroscopy.

.c2.1.2. History of Study Area

.c3.1.2.1. Background Information

Biscayne Bay is a large lagoonal system located on the southeast coast
of Florida. The Bay is unique in many ways. It offers a large,
year-round protected body of water, with a great diversity of natural
resources, close to a major metropolitan area and has retained to a
large degree, in its southern extremities, a character of undisturbed
tropical naturalness. Economically the surrounding areas are dependent
on the Bay. The local economy is tourism based and dependent on climate
and esthetics (Thorhaug, 1977). The Bay plays a very important role in
this economy by supplying esthetics and both extensive recreational and
commercial activities. The Bay is unique in another very important area
best defined as user awareness and concern. This is exemplified by the
establishment of the Biscayne Bay Management Plan.

Since the founding of the City of Miami in 1896, the northern and
central portions of the Bay have undergone extensive physical,
biological and chemical alterations. These alterations are the direct
result of unmanaged and inadequately planned urbanization, dredge and
fill activities, channelization, water management techniques and changes
in the natural shoreline. During the mid to late seventies, great
concern arose as to the future of Biscayne Bay. Past uses of the
shoreline had resulted in habitat destruction, water pollution and lack
of public access. To rectify these problems and abate many of the future
problems caused by the increasing use pressure of the Bay the Board of
County Commissioners, in 1978, declared Biscayne Bay an \"Aquatic Park
and Conservation Area\". In conjunction with the declaration, monies
were appropriated to develop a management plan to guide the Bay\'s
future and clarify and consolidate

the jurisdictional controls over the Bay and its shorelines. Since the
completion of the management plan in March of 1981, the local county
government has actively pursued establishing baseline data and the
development and refinement of management protocols for the Bay.

The increasing growth of Dade County, the expansion of the Port of Miami
for the purpose of handling more and larger shipping traffic, and
increasing use of the port facilities of the Miami River have caused a
constant increase in the input of anthropogenic petroleum products to
the Bay and has substantially raised the possibilities of a major oil
spill within the Bay proper.

A vessel traffic study conducted in 1976 by the U.S. Coast Guard showed
an average of 38 oil-carrying tanker vessels per day transported over a
million tons of crude oil per day within 5 to 25 miles of the southern
Florida coastline.

The study also identified the major vessel traffic lanes. There are
three crossing and merging areas located near southern Florida. The
approximate location of these areas are: 13 miles south-southeast of
Miami; 14 miles south of the Dry Tortugas; and 13 miles south-southeast
of West Palm Beach. These areas, where major traffic lanes cross and
merge, increase the possibility of collisions and spills.

Many vessels stay within coastal waters and utilize the Intracoastal
Waterway (ICW) to avoid Gulf Stream currents and rough waters. Wilson
(1975) estimated that 3 million tons of cargo were shipped via the ICW
and Biscayne Bay. Fuel oil leads all of those commodities shipped in
volume.

The recent planned exploration for offshore oil and the increased
production in the Gulf of Mexico, Caribbean Sea and Mexico, the
continuous growth of the Dade County economy and its rapid movement
towards becoming a major trade center has unquestionably caused an
increase in the tanker traffic off the southern Florida coast and within
the coastal zone during the last several years. This substantially
increases the probability of collisions, groundings and oil spills
within southern Florida and the Biscayne Bay area.

.c3.1.2.2. Geography

Biscayne Bay is classified as a shallow, semi-tropical lagoon (Roessler
and Beardsley, 1975). The Bay covers 573 km2 (W. Campos, per. com.), is
north-south tending, approximately 56 km in length and averages 8 km in
width with a maximum width of about 16 km. The average depth is
approximately 1.8 m with a maximum depth of 4 m (Roessler and Beardsley,
1975) except in dredged areas where depths are reported to exceed 12 m.
The major tributaries are Arch Canal, Biscayne Canal, Little River,
Miami River, Coral Gables Waterway, Snapper Creek, Black Creek, Goulds
Canal, North Canal, Florida City Canal, and the Model Land Canal. The
Miami River has the largest input into the Bay and averages 18 m3/sec
(Wilson, 1975).

The Bay is bound on the north by Dumfoundling Bay, which was
historically a shallow water marsh, and on the south by Card Sound. The
western side includes the mainland (Miami and suburbs) and to the
southwest the Everglades. The eastern border is formed by sedimentary
barrier islands (Miami Beach) to the north, and to the south a tidal bar
belt (Safety Valve) and a continuous line of bedrock islands (Florida
Keys) (Wanless, 1976).

The system was originally a freshwater basin until about 4,000 years
ago, when the gradual rise in sea level inundated the area. The majority
of the freshwater input during this time was by overland flow and
groundwater seepage from adjacent uplands. As recently as the 19th
century, freshwater marshes bordered the western side and freshwater
springs flowed within the Bay. The input of freshwater declined as
upland areas were drained and overland flow was

altered by urban and agricultural development (Thorhaug, 1977).
Accompanying this decrease in freshwater was an increase in saline water
input caused by openings cut in the barrier islands to facilitate access
to the Bay by ships. This resulted in an increase in the salinity of the
Bay and a change from a typical bar-built estuary with a shoreline
dominated by freshwater marshes to a subtropical lagoon with mangrove
fringed shorelines.

For descriptive purposes the Bay is divided into three basins separated
by both natural and man-made structures (Wilson, 1975). The north basin
extends from Dumfoundling Bay south to the Rickenbacker Causeway;
central basin from the Rickenbacker Causeway south to Featherbed Bank;
the southern basin extends from Featherbed Bank to the Arsenicker Keys.

The north basin has been, for all practical purposes, totally developed.
The area is bordered on the east by the barrier islands of Miami Beach
and Virginia Key, and on the west by developed shorelines. In excess of
40% of this area has been either dredged or filled (Biscayne Bay
Management Plan, 1981) and the shoreline is almost completely seawalled
(Roessler and Beardsley, 1975). Located within this area is the Port of
Miami and the Miami River where on and off loading of cargo, ship
building and repair take place and many industrial complexes are
located.

The central basin is commonly considered a transition zone between the
heavily urbanized areas of the north basin and the relatively
undeveloped southern portions of the Bay. This area contains several
large marinas and is used for commercial and recreational purposes.

The southern basin is relatively pristine although several canal systems
draining urban and agricultural areas empty into it. This area contains
the Biscayne National Park. The Park was originally established in 1968
as the Biscayne National Monument and covers 390 km2. Most of the
mangrove shoreline is still relatively intact. The only prominent
man-made structures visible from this area are the Cutler and Turkey
Point power plants.

.c3.1.2.3. Climatic Conditions

The low latitude of southeastern Florida, and its proximity to the
Atlantic Ocean and Gulf Stream, produce a subtropical marine climate
characterized by very mild winters and warm summers. The mean annual air
temperature for Miami is 24 °C (Veri *et al.*, 1975) and ranges from a
low of 18 °C in January to a high of 32 °C in August. The average annual
precipitation is 1524 mm (Buston, 1962) of which 73% falls during the
summer months (May to October). Prevailing moderate winds are easterly
and southeasterly and approach the mainland from over the water. These
sea breezes help to temper the climate.

> .c3.1.2.4. Ecology

Biscayne Bay is shallow throughout, vertical stratification is rare and
circulation is predominantly one layer (Lee, 1975). The tides are
semidiurnal and have a mean tidal range of 0.76 m at the Port of Miami
entrance. This tidal amplitude decreases to the south reaching 0.22 m in
Card Sound (Schneider, 1969). Input of coastal waters to the Bay occur
through tidal channels (Baker\'s Haulover, Government Cut, Norris Cut,
Bear Cut, The Safety Valve, Sands Cut, Caesar\'s Creek, Broad Creek and
Angelfish Creek) along its eastern edge. The freshwater inputs are
introduced via small mainland rivers, creeks, canals, groundwater
percolation and rainfall.

Water temperatures average approximately 17 °C during the winter and 31
°C in the summer. Extremes measured during a 5 year study were 9 °C to
35 °C at shallow water stations (Roessler and Beardsley, 1975).

Salinity of the Bay is influenced by rainfall, although this
relationship is modified when the flood gates of the numerous drainage
canals are opened. During the wet season the salinity gradient of the
Bay increases from west to east. This situation can be reversed though
during periods of drought.

The bottom communities of the Bay have recently been surveyed
extensively and mapped by the Dade County Department of Environmental
Resources Management (G. Milano, pers. com.). This information reveals
that the majority of the bay bottom consists of mixed seagrasses
(*Thalassia testudinum,* *Syringodium filiforme* and *Halodule
wrightii*). Other large areas of the bay bottom consist of a mixture of
seagrasses and hard bottom communities (soft corals and/or sponges).

The Bay is populated with 468 species of fishes representing 71
families. Ninety species are of commercial importance, 89 are considered
to be sport fishes, and 128 are important forage fishes. The commercial
species are predominantly invertebrates, and include shrimp, spiny
lobster, stone crab, and blue crab. Sport fishing consists mainly of the
Spanish mackerel, grunts, crevalle jack, snappers, king mackerel,
bluefish, sea trout, snook, tarpon and bonefish (de Sylva, 1970).

> .c3.1.2.5. Economy

It was estimated in 1975 that the local marine industry, which includes
shipping, cruise lines, boat manufacture, sales and service, shipyards,
marinas, bait and tackle shops, etc., contribute 20% to the Dade County
economy. This ranks it third in economic importance preceded by tourism
and the airlines. Dade County\'s main harbor facilities are the Port of
Miami and the Miami River. The Port of Miami leads all Florida ports in
dollar value of imports and exports. In 1973, the combined ports handled
in excess of 8 million tons of freight. Incoming cargo consists mainly
of fuel oil and gasoline, foodstuffs and raw materials while outgoing
cargo consists of manufactured goods, locally produced agricultural
products and foodstuffs bound for Caribbean islands and Latin America.
Approximately 3 million tons of freight is shipped between Jacksonville,
Miami, and Key West via Biscayne Bay and the Intracoastal Waterway. Fuel
oil leads all other commodities shipped via this route in volume.

The commercial fisheries of the Bay are dominated by the live bait
shrimp industry which in 1975 had a wholesale value of \$640,000
followed by dead shrimp (\$23,700) (Wilson, 1975). Large quantities of
shellfish are also landed in Dade County but the majority of these are
caught in areas other than Biscayne Bay.

.c1.2. Methods

.c2.2.1. Study Area Location

Biscayne Bay is located along the southeast coast of Florida (Figure 1).
The study area extended from Dumfoundling Bay (lat. 25° 58\' N; long.
80° 15\' W.) to Card Sound (lat. 25° 24\' N; long. 80° 17\' W). The
study area is contained almost entirely within Dade County. Only its
most northerly and southerly extremities extend into Broward and Monroe
Counties, respectively.

.c3.2.1.1. Sample Station Locations

One hundred fifty-five stations were sampled for bottom sediments in
Biscayne Bay during the first year of the study. Figure 1 presents their
location and Appendix A gives the latitude, longitude and coring method
used. The location of each sampling station was chosen by assessing
multiple criteria relating to its usage by man and other biotic and
abiotic parameters. A detailed description of the selection criteria
used is presented in the following section.

Sampling stations for the second year of the study were located in the
Little River, Miami River, Snapper Creek, Goulds Canal, Black Creek and
Military Canal. These areas are outlined on Figure 2 and the sampling
stations occupied for water and sediment collections are indicated.
Appendix B lists the latitude, longitude, type of sample (water and/or
sediment) and method of coring used. \[FIGURE 2 IS MISSING IN THE
ORIGINAL.\]

> .c3.2.1.2. Criteria for Station Selection

The sediment collection sites for the first year of the study were
selected by incorporating criteria relating to the physical, chemical,
and biological processes and man\'s historical, present and future usage
of the Bay. The second year study focused on areas where petroleum
contaminants had been identified during the first year of research.

The selection criteria for sample stations for the first year involved a
review of the available scientific literature concerning hydrocarbons in
general and Biscayne Bay in particular (see Appendix C). In addition,
consultations with research faculty, local, county, state and federal
agencies were conducted. These tasks produced a great deal of useful
information which was synthesized into a set of selection criteria.
These criteria are discussed below and summarized as to their
relationship to the sample collection stations in Table 1.

.c4.2.1.2.1. Previous Studies and Dade County Water Quality Monitoring
Stations

Previous studies of the pollution problems of Biscayne Bay have been
centered within the confines of the northern basin (Hela *et al.*, 1957;
McNulty, 1961, 1970; Austin, 1971; D\'Amato, 1973; Buck, 1976; Sigel *et
al.*, 1976; Voss, 1976; Thorhaug *et al.*, 1976; Waite, 1976). Although
most of these studies are well documented this area has been extensively
dredged and many of the sampling stations used in previous studies are
no longer there. The areas not effected by dredging or other activities
were incorporated within the sampling program.

In 1978, the Dade County Department of Environmental Resources
Management began monitoring the water quality at 48 stations positioned
throughout Biscayne Bay. To augment this database sample stations for
this project were positioned on or near pre-existing county stations.

.c4.2.1.2.2. Oil Sensitivity Index

The distribution of oil-sensitive coastal resources in south Florida has
been determined by the South Florida Regional Planning Council (1981)
using a mapping system incorporating an Environmental Sensitivity Index
(ESI) developed by Gundlack and Hayes (1978). The ESI integrates natural
and man-made geomorphic features with biological and living resources
(e.g., nesting sites, rookeries) information to rank environments by
their sensitivity. The ranking ranges from I to 10, with 1 being the
least sensitive (exposed vertical rocky shores and seawalls) and 10
(mangroves) being the most sensitive. Sampling stations have been
established along shorelines with an ESI of 8 or higher (8 = sheltered
rocky shores and seawalls, 9 = sheltered tidal flats, 10a = mangroves,
10b = sheltered mangroves).

![](media/image7.pct){width="3.5277777777777777in"
height="8.708333333333334in"}

.c7.Figure 1. Biscayne Bay study area and sampling station locations for
the Year 01 study.

.c8.Table 1. Criteria used in selecting the first year\'s sediment
sampling stations.

> PS = previous studies; CS = Dade County water quality station; 0SI =
> oil sensitivity index; ST = sediment type; VT = vegetation type; C =
> circulation; Sl = supra and intertidal areas; BF = boating facilities;
> PBF = proposed boating facilities; DDR = boating departure and
> destination routes; PA = preferred anchorage; DED = dredge, spoil,
> erosional or depositional area; LU = Iand usage.
>
> SELECTION CRITERIA
>
> Sample \# PS CS SO ST VT C IS BF PBF DDR PA DED LU
>
> 1 X X X
>
> 2 X X X
>
> 3 X X
>
> 4 X X
>
> 5 X X X X
>
> 6 X X X
>
> 7 X X X
>
> 8 X X X
>
> 9 X X X
>
> 10 X X
>
> 11 X X
>
> 12 X X X
>
> 13 X X X X
>
> 14 X X X
>
> 15 X X X
>
> 16 X X X X
>
> 17 X X X X
>
> 18 X X X
>
> 19 X
>
> 20 X X X
>
> 21 X X
>
> 22 X
>
> 23 X
>
> 24 X X
>
> 25 X X
>
> 26 X
>
> 27 X X X
>
> 28 X
>
> 29 X X
>
> 30 X X X
>
> 31 X
>
> 32 X X
>
> 33 X X
>
> 34 X X
>
> 35 X X
>
> 36 X X
>
> 37 X X X
>
> 38 X X
>
> 39 X X X
>
> 40 X X

Table 1. Criteria used in selecting the first year\'s sediment sampling
stations (cont).

> PS = previous studies; CS = Dade County water quality station; 0SI =
> oil sensitivity index; ST = sediment type; VT = vegetation type; C =
> circulation; Sl = supra and intertidal areas; BF = boating facilities;
> PBF = proposed boating facilities; DDR = boating departure and
> destination routes; PA = preferred anchorage; DED = dredge, spoil,
> erosional or depositional area; LU = Iand usage.
>
> SELECTION CRITERIA
>
> Sample \# PS CS SO ST VT C IS BF PBF DDR PA DED LU
>
> 41 X X X
>
> 42 X
>
> 43 X X X
>
> 44 X X X X X X
>
> 45 X X X X
>
> 46 X X X
>
> 47 X X X
>
> 48 X X X
>
> 49 X
>
> 50 X X
>
> 51 X X X X
>
> 52 X X X
>
> 53 X X
>
> 54 X X X
>
> 55 X X X
>
> 56 X X X
>
> 57 X X X
>
> 58 X X X
>
> 59 X X X
>
> 60 X X X
>
> 61 X X X
>
> 62 X X X
>
> 63 X X X X
>
> 64 X X X X X
>
> 65 X X
>
> 66 X X X X X
>
> 67 X X
>
> 68 X X
>
> 69 X X
>
> 70 X X
>
> 71 X X
>
> 72 X X X X X
>
> 73 X X X X X
>
> 74 X X X
>
> 75 X
>
> 76 X
>
> 77 X X X X
>
> 78 X X X
>
> 79 X X X
>
> 80 X X

Table 1. Criteria used in selecting the first year\'s sediment sampling
stations (cont).

> PS = previous studies; CS = Dade County water quality station; 0SI =
> oil sensitivity index; ST = sediment type; VT = vegetation type; C =
> circulation; Sl = supra and intertidal areas; BF = boating facilities;
> PBF = proposed boating facilities; DDR = boating departure and
> destination routes; PA = preferred anchorage; DED = dredge, spoil,
> erosional or depositional area; LU = Iand usage.
>
> SELECTION CRITERIA
>
> Sample \# PS CS SO ST VT C IS BF PBF DDR PA DED LU
>
> 81 X X X
>
> 82 X X
>
> 83 X
>
> 84 X X
>
> 85 X X
>
> 86 X
>
> 87 X X
>
> 88 X X
>
> 89 X X X
>
> 90 X
>
> 91 X X X
>
> 92 X X X
>
> 93 X X X X
>
> 94 X X X X X
>
> 95 X X X X X X
>
> 96 X X X X
>
> 97 X
>
> 98 X X
>
> 99 X X X X
>
> 100 X X
>
> 101 X X X X X
>
> 102 X
>
> 103 X X
>
> 104 X X X
>
> 105 X
>
> 106 X
>
> 107 X X X
>
> 108 X X
>
> 109 X X X X
>
> 110 X
>
> 111 X
>
> 112 X X X X
>
> 113 X X X
>
> 114 X X X X
>
> 115 X X X X
>
> 116 X X
>
> 117 X X X
>
> 118 X X X
>
> 119 X X X
>
> 120 X X

Table 1. Criteria used in selecting the first year\'s sediment sampling
stations (cont).

> PS = previous studies; CS = Dade County water quality station; 0SI =
> oil sensitivity index; ST = sediment type; VT = vegetation type; C =
> circulation; Sl = supra and intertidal areas; BF = boating facilities;
> PBF = proposed boating facilities; DDR = boating departure and
> destination routes; PA = preferred anchorage; DED = dredge, spoil,
> erosional or depositional area; LU = Iand usage.
>
> SELECTION CRITERIA
>
> Sample \# PS CS SO ST VT C IS BF PBF DDR PA DED LU
>
> 121 X X
>
> 122 X
>
> 123 X X X
>
> 124 X
>
> 125 X X X X
>
> 126 X X X
>
> 127 X X
>
> 128 X X
>
> 129 X X X
>
> 130 X X X
>
> 131 X
>
> 132 X
>
> 133 X X X X
>
> 134 X X X
>
> 135 X X
>
> 136 X X X X
>
> 137 X X X X
>
> 138 X X
>
> 139 X X X
>
> 140 X X X
>
> 141 X X
>
> 142 X X
>
> 143 X X
>
> 144 X X
>
> 145 X X X
>
> 146 X X X X
>
> 147 X X
>
> 148 X X X
>
> 149 X X
>
> 150 X X
>
> 151 X X X
>
> 152 X X X
>
> 153 X X
>
> 154 X
>
> 155 X X X
>
> 156 X X

.c4.2.1.2.3. Sediment Type

Areas of the Bay exhibiting different sediment types were evaluated for
sampling using three criteria. These were: thickness of substrate,
amount of organic material, and particle size distribution.

The sediment depth in Biscayne Bay is highly variable and in many areas
less than 1 m (Wanless, 1976). Sediment build-ups, which are present,
form distinct patch-like accumulations and are controlled by several
factors (i.e., wind, dredging, currents and storm events). Six major
recent sediment regimes have been recognized by Wanless (1976) based on
sediment type, body geometry and depositional controls. Areas
representative of these regimes as well as transitional areas were
sampled.

The deposition and incorporation of petroleum hydrocarbons into marine
sediments is well established in the literature (Blumer and Sass, 1972;
Clark, 1966; Farrington, 1980; LaFlamme and Hites, 1978; National
Academy of Sciences, 1975; Zafiriou, 1973). The amount of *n*-alkanes
sorbed by marine sediments has been shown by Meyers (1975) to be
dependent on sediment particle size. The smaller the particle size the
greater the sorption of hydrocarbons. Samples were collected which
incorporated sediments of different particle sizes.

The affinity of petroleum hydrocarbons for organic compounds has been
investigated by Meyers and Quinn (1973) who suggest that organic matter
may mask sorption sites in sediment, thereby reducing the available
surface area for sorption of petroleum components. Suess (1968) states
that an organic material coating on particles will enhance the sorption
process by providing a lipophilic layer. Thus the organic content of the
sediment has an important effect on its uptake of petroleum. Sediment
samples were collected from environments which contained variable
concentrations of organic matter. These ranged from relatively
organic-free quartz sands to highly organic peat substrates.

.c4.2.1.2.4. Vegetation Type

Forty-three percent of the Bay bottom is covered with seagrasses
(Snedaker and Brook, 1976). The majority of the seagrasses are
*Thalassia testudinum* (turtle grass), *Halodule* *wrightii* (Cuban
shoal grass) and *Syringodium filiforme* (manatee grass). The primary
functions of these plants are: 1) food source; 2) shelter and
protection; 3) sediment stabilizer; and 4) a chemical sink in terms of
nutrient cycling (Thorhaug *et al.*, 1976). The environmental health of
Biscayne Bay is linked directly to these seagrass communities which are
relatively sensitive to pollution. The effect of pollutants on seagrass
often results in mortality, thus causing the whole community dependent
on them to disappear (Thorhaug *et al.*, 1976). A representative number
of samples incorporating different types to vegetation were included in
the sampling program.

.c4.2.1.2.5. Circulation

The dominant exchange mechanisms within the Bay are wind and the
semidiurnal tides (Lee and Rooth, 1973). Tidal current velocities
through passes along the eastern side of Biscayne Bay average 25 to 100
cm/sec (Hela *et al.* 1957). Within the Bay, tidal currents are less
than 50 cm/sec while portions of the southwestern margin appear isolated
from tidal circulation (Weiss, 1948). Several nodal points of tidal
convergence are recognized within North Bay, between 49th Street and
79th Street Causeways (Lee and Rooth, 1973). Samples from areas of
maximum and minimum exchange were collected.

.c4.2.1.2.6. Supratidal and Intertidal Areas

The stranding of pelagic and coastal oil slicks and tar balls is
generally restricted to supratidal and intertidal environments. Oil
coverage in these environments is controlled by the slope of the exposed
area, with maximum amount accumulating on gently sloping or flat
surfaces. Sediment samples representative of major intertidal
environments such as the Safety Valve, Featherbed Banks, Arsenicker
Keys, Middle Ground Shoals and mangrove shorelines were collected.

.c4.2.1.2.7. Boating Facilities

A unique combination of climate, urban and physical geographic features
permit year round public access to all types of boating related
activities within Biscayne Bay. In 1975-1976, there were over 250,000
recreational boating trips made from Dade County, approximately 187,500
were made within the Bay (Austin, 1971). Support facilities such as
marinas and launching ramps are an integral part of recreational as well
as commercial activities. In 1981, there were 78 marinas and 5 ramps
marginal to Biscayne Bay (Biscayne Bay Management Plan, 1981). In many
instances, boat maintenance and repair operations release paint, oil and
grease into bay waters. Boyd (1976) estimates that 1% of all coastal oil
pollution results from the activity of marina facilities. Marinas,
harbor facilities, and other marine related industries were sampled.

> .c4.2.1.2.8. Proposed Boating Facilities

Dade County Department of Environmental Resources Management estimates
that 42 additional support facilities and 42 additional marinas with wet
berths for recreational and commercial boaters are planned for
construction in Biscayne Bay. Seven are presently under construction.
The location of existing and planned boating facilities were
incorporated in sample site selection.

.c4.2.1.2.9. Boating Departure Routes and Destinations

The Intracoastal Waterway and privately dredged channels are major
thoroughfares for industrial, commercial and recreational transport
throughout Biscayne Bay. As stated earlier, 3 million tons of cargo were
transported in this manner, with the majority of it being fuel oil
(Wilson, 1975). Channel sediments, resuspended by boat wakes, prop wash
and hull scrapes may incorporate surface oil slicks into bottom
deposits. This mechanism may result in elevated concentrations of
petroleum hydrocarbons between commonly traveled departure and
destination routes. Sampling stations were established along all major
marine routes.

.c4.2.1.2.10. Preferred Anchorage

The recreational features of Biscayne Bay accessible by boat are
numerous. Most of these are located along the southern boundaries of the
Bay. The preferred anchorages at these sites are of interest for
monitoring the effects of recreational boating on petroleum hydrocarbon
distribution.

.c4.2.1.2.11. Dredging, Spoil, Erosional and Depositional Areas

Man-made holes and canals marginal to Biscayne Bay appear to contain
complete sequences of layered sediment that have accumulated since their
construction (Harlem, 1979). Once sediments are deposited in the
patchwork of deep dredge holes they are less susceptible to
resuspension. It is likely these areas may be prominent sinks for
pollutants in particulate form. Several of these areas were incorporated
into the sampling program.

The scouring and redistribution of contaminated sediments is an
important mechanism of pollutant transport. Dredging, winter cold
fronts, and hurricanes are the principal agents of sediment transport
within the Bay. The strong northerly winds of cold fronts cause the
redistribution of fine sediments and the southward transport of
unstabilized sands on the Bay bottom (Warzeski, 1976). The sedimentary
effects of hurricanes are more pronounced due to the far greater energy
of hurricane winds. These storms can remove or deposit centuries of
sediment accumulations in one single event thus, the classification of
environments as erosional or depositional is necessary to accurately
interpret the spatial distribution of the sediment analysis. Samples
from both erosional and depositional environments were collected.

.c4.2.1.2.12. Land Use

Between the years 1896 to 1950, the process of urban settlement about
Biscayne Bay was rapid and often unplanned (Prestamo and Greenan, 1976).
During these 54 years, the conversion of agricultural land to
residential use established the present urban distribution pattern.
Within the past 30 years the urban process has become the development of
open land with very few cases of redevelopment. The effects of
urbanization on surface hydrology have been two fold (Delleur, 1981).
The first factor is the covering of parts of the catchment (substrate)
with impervious surfaces such as roofs, streets, sidewalks and parking
lots. Dust, dirt, sediments and pollutants of various kinds, settled
from the atmosphere and generated by the urban activities, accumulate on
these impervious areas between storm events and are eventually washed
into the Bay by runoff during rains and storm events.

The second factor effecting the urban runoff process is a result of the
improvement of the hydraulic efficiency of the drainage network through
the straightening and lining of channels, construction of sewers and
culverts. The increased flow velocities enhance the transport of
suspended solids and pollutants. The pollutant loading at the downstream
end (the Bay) of the urban runoff conveyance is thus increased. To
assess the impact of urbanization, stations were located within and
around urban developments and their drainage areas.

.c3.2.1.3. Collections

In the two-year program, sediment samples were collected by three
different coring techniques: vibra, remote and push. During first year,
in order to obtain a good spatial coverage of the Biscayne Bay lagoonal
systems, a total of 156 cores were collected, this included 15 vibra
cores, 47 remote cores, 62 short push cores, and 32 long push cores. In
the second year, the goal was to investigate and to quantify the areas
of high petroleum contamination found during the first year. Thus, 22
cores in three selected areas were obtained, 19 remote cores and 3 short
push cores. Replicate cores within a square meter of each other were
collected at every station during the first year study. The sediment
samples for intercalibration were grab samples collected outside
Biscayne Bay in deep water southeast of Miami. Except for
intercalibration samples, Figure 3 indicates the steps followed for each
core from collection to analysis. The intercalibration samples which
were collected with a Peterson dredge, were placed in jars, covered with
aluminum foil, capped, labeled and carried on ice from ship to freezer.

Biological samples were collected in cooperation with the Fisheries and
Habitat Management of Biscayne Bay study conducted by the Rosenstiel
School of Marine and Atmospheric Science and funded by the Dade County
Department of Environmental Resources Management. All samples, after
collection, were stored under lock and key, subsampled and analyzed
using procedures, methodologies and quality assurance programs which
guaranteed court competence and minimized contamination.

![](media/image8.pct){width="5.180555555555555in"
height="5.916666666666667in"}

.c7.Figure 3. Flow diagram of sample collection and storage procedures.

The core tube assembly, used for all sediment collections, consisted of
7.6-cm diameter aluminum irrigation tubing, 7.8 cm diameter circular,
aluminum liner plates, and 7.5-cm plastic core caps. Prior to use, all
core tubes, after being cut to the appropriate length, and liner plates
were washed with Alconox, rinsed with tap water and burned at 500 °C in
a kiln to remove all organic contaminants. When cooled, the tubing was
sealed by securing aluminum foil over both ends of the core tube. The
circular liner plates were fitted into the caps and then secured to both
ends of the core tube.

Short cores were obtained when sediment thickness was less than 20 cm.
The tube was submerged and the core caps were removed. The short tubes
were inserted by hand to bedrock, capped, withdrawn from the sediment
and transported to the surface in an upright position.

Long 1.3-m push cores were collected by securing a pair of adjustable
\"T\" handles near the top of the capped core tubes. The core caps were
removed only when the apparatus was submerged below the surface (micro)
layer. The tube was pushed into the sediment, the aluminum lined caps
were placed over the top of the core tube prior to, and under the core
tube bottom after removal from the sediment.

Areas that represented possible health hazards to divers were sampled by
remote coring. This process involved the use of 1.3 m length of aluminum
core tubing connected to a reusable extender, equipped with a one-way
valve. The sampling device was pushed into no more than I m of sediment
and the valve was closed by inserting a hexane-rinsed stainless steel
sphere (7 cm diameter) into the extension tube. During the extraction of
the core tube from the sediment the sphere created a vacuum which
retained the sediment in the tube until capped at the surface. The
remote coring method was preferred to Box coring and Grab sampling
because, 1) possible sample exposure to contaminants emanating from the
sampling vessel were eliminated; 2) possible sample exposure to surface
films and water-borne pollutants that may be present at sample locations
were eliminated; 3) the sample does not contact any lubricated moving
parts; 4) undisturbed surface samples are easily and quantitatively
obtained.

Sediment samples that required penetration to intercept deeper
depositional layers predating anthropogenic impacts were attained by
using a portable vibra core system (Lanesky, 1979). The system consisted
of a vibrating head, mounted perpendicular to the top of a cleaned
aluminum core tube, that initiated a low amplitude standing wave. This
standing wave fluidized and displaced the sediments adjacent to the core
tube and allowed it to pass through the sediment with minimal
resistance. Core recovery averaged between 90 and 100%. Actual coring
time ranged from 0.5 to 5 minutes. Preservation of fine laminations and
cross stratification in x-ray radiographs and slabbed, impregnated cores
showed that this technique gave minimal distortion along the core tube
walls (Lanesky, 1979).

After collection the core tubes and caps were coded, sealed with tape,
signed and dated. Any undue disturbance during this process necessitated
repeating the procedure until intact samples were obtained.

At each station the latitude and longitude in degrees, minutes and
seconds as well as the proximity of navigational and prominent
landmarks, were recorded in permanently bound, waterproof field
notebooks. Station number, sample number, date, time, water and air
temperature, bottom type, salinity, water depth and coring method were
also recorded. Prior to station departure, the supervising individual
checked the log book and the sample to verify that they had been
collected, identified and sealed correctly. At the end of each day\'s
notes the page was signed and dated by the person who performed the
work. The team leader checked all notes for accuracy, correct transfer
of data, completeness, legibility and neatness.

Upon arrival at the laboratory the sealed and coded samples were
transferred by project personnel to a core locker maintained at 4 °C,
secured in an upright position and kept under lock and key.

Within 48 hours of collection the water above the sediment in the core
tubes was removed with a large clean pipette. Once the water had been
removed the core tubes were split by making two shallow longitudinal
slices with an electrical circular saw. Samples for petroleum
hydrocarbon analyses were collected by sub sampling from only the center
of the core. This was done by removing a 5 cm long cylinder shaped
subsample, with hexane rinsed stainless steel spatulas, and placing it
on clean aluminum foil. An inner 2 cm diameter plug was removed by
inserting a cleaned, organic-free 50 mL glass beaker through the center
of the subsample. The sample was placed in a organic-free glass jar and
covered with a foil lined screw top. It was then transferred to a locked
freezer maintained at - 20 °C until extracted.

The thin layer from the outside of the remaining sediment was shaved
away and the remains were placed in a similar glass container for
sediment grain size and organic analysis. These samples were also stored
at -20 °C in a locked freezer.

Biological samples for the duration of the two year project were
collected in cooperation with Mr. Steve Berkeley, Principal Investigator
for the Fisheries and Habitat Management of Biscayne Bay study. Samples
were collected by trawl and traps in northern, central and southern
areas of the Bay. In addition, during the second year study, samples
were collected when available from the five study areas. Immediately
upon collection samples were wrapped in aluminum foil, labeled (species,
number, time, date, collection area and method), sealed in a plastic bag
and placed on ice. After returning to the laboratory the samples were
placed under lock and key in a freezer maintained at -20 °C until
analysis could be completed.

The water samples, that were examined for hydrocarbons during the second
year program, were collected in 19-liter glass bottles. To obtain these
samples, the glass bottles were placed in a wooden frame, covered with a
fitted wooden cover secured into place with eye bolts and stoppered with
an aluminum covered stopper fitted with an eye-bolt. Before lowering
this sampler into the sea, a lanyard was run through the eye bolts and
secured to the winch cable, a long cord was fastened to the eye-bolt in
the stopper and a lead weight was attached to the bottom of the frame.
With the winch the BC (Brown-Corcoran) sampler was lowered into the sea
to the desired depth, and the stopper was removed by pulling the cord.
When the bottle was filled with water, the sampler was raised to just
below the surface stoppered with an aluminum covered stopper, and then
brought aboard. Here it was labeled, sealed and set aside for later
analysis in the laboratory.

.c3.2.1.4. Quality Assurance

Great care was taken during the sampling and subsampling process to
insure that contamination was kept to a minimum and chain of custody was
maintained. This was accomplished by adhering to strict clean
procedures, keeping all samples under lock and key and maintaining
detailed field and laboratory records.

The core tubes were washed, rinsed in tap water and burned at 500 °C in
a kiln to remove any sources of organic contamination. Immediately after
being removed from the kiln the core tubes were sealed with clean
aluminum foil. The foil was secured in place with plastic core caps
lined with aluminum discs that had been cleaned using the same procedure
as the core tubes. This insured a contaminant free container for sample
collection.

During collection of the sediment samples the core tubes were kept
sealed until they were fully submerged, this minimized any contamination
by the water column and/or surface micro layer.

The collected cores were resealed with the foil and aluminum disc lined
plastic core caps immediately after collection. Care was taken to keep
the collected samples in a vertical position at all times to maintain
its internal integrity. Immediately after being brought on board the
support vessel the plastic caps were secured with tape to the core tube.
This prevented the sample from falling out of the collection tube and
also secured the sample against tampering. The core was labeled as to
station number, top and bottom. Replicate cores were taken at each
station within one meter of each other. This supplied a complete set of
replicate cores from all the sampling stations should they be needed.
The collected cores were under the direct responsibility and supervision
of the field supervisor during collection and storage.

The samples were returned to the laboratory and transferred directly to
a locked, refrigerated core locker. The samples were stored in an
upright position until they could be subsampled. All materials coming
into contact with the samples during subsampling were either hexane
rinsed or burned at 500 °C to remove organic contaminants. The subsample
fractions (for hydrocarbon, grain size and organic analysis) were stored
in burned, glass screw top jars with aluminum foil liners. The jars were
stored in a locked freezer at -20 °C until analysis could be performed.

Biota samples were collected using both trawl and traps. Immediately
after removing the specimen from the collection device it was wrapped in
clean aluminum foil and labeled as to time, date, method and location.
The specimen was then placed in a plastic bag which was sealed with
tape. This secured and the sample from any contamination and tampering.
The sample was then placed on ice until transported to the laboratory.
On arrival at the laboratory the samples were stored in a locked freezer
maintained at -20 °C.

The water samples were brought to the laboratory and extracted
immediately if possible. If there were more samples than could be
extracted at once, they were kept sealed and stored in a cold room at 4
°C. Holding time was not more than 48 hours.

.c2.2.2. Sediment Grain Size Analysis

A representative subsample of the collected surface sediments was
analyzed for grain-size fractions and distribution. The samples were
freeze-dried in a Virtis Model No. 10-146-MB-BA freeze dryer. A
representative subsample was obtained by recovering 35 [+]{.underline} 5
g from a Jones-type, H. W. Curtin sediment splitter. The samples were
fractionated into three size classes, \>2000 µ (gravel), 2000 to \>63 µ
(sand), and \<63 µ (silt-clay) by mechanically dry sieving for 15 mins.
through 2000-µ and 63-µ sieves.

The \>2000 µ fraction (gravel) was dried at 105 °C to a constant weight,
cooled to room temperature in a desiccator, weighed and archived. The
\<63 µ fraction was transferred into a labeled one-liter cylinder. The
2000 µ to \>63 µ fraction was mixed with a 4% (w/v) solution of sodium
hexametaphospate and placed in a Bransonic 12 sonic bath for 15 mins.
After sonification this fraction was rinsed onto a 63-µ sieve with one
liter of distilled water. The particles which passed through the 63-µ
sieve were combined with the \<63 µ previously stored in the labeled,
one liter cylinder. The \<63 µ fraction was transferred to a labeled
aluminum weighing dish, dried to a constant weight at 105 °C, cooled to
room temperature in a desiccator, and weighed.

The weight of the \<63 µ fraction was calculated by subtracting the sum
of the \>2000 µ and the 2000 µ - \>63 µ fraction weights from the total
sample weight. From this data, dry weight percentages for gravel (\>2000
µ), sand (2000 to \>63 µ), and silt-clay (\<63 µp) fractions were
calculated.

.c2.2.3. Organic and Carbonate Content Analysis

The determination of the total organic matter and carbonate content of
the sediments was performed by using a modified version of Galle and
Runnel\'s (1960) weight loss on ignition process. The procedure uses a
high temperature muffle furnace to oxidize both organic matter and
carbonate. This method has been proven to be 100% efficient for the
recovery of total organic matter and carbonate bearing minerals in
modern marine sediments (Byers *et al.*, 1978; Dean, 1974). However,
this analysis does not distinguish between magnesium (Mg), strontium
(Sr) and calcium (Ca) bearing carbonate minerals. It has been reported
(Wanless, 1976) that of the carbonate bearing minerals in Biscayne Bay,
calcium carbonate (CaC03) is significantly more abundant. Therefore, all
carbonate values are reported as percent calcium carbonate.

Freeze dried, representative quantitative subsamples were obtained by
using a Jones-type, H. W. Curtin sediment splitter. The split samples
were stored in clean 25 mL Erlenmeyer flasks, oven dried at 105 °C to a
constant weight and cooled to room temperature in a desiccator. A sample
of approximately 10 g was transferred into a ceramic crucible of known
weight. The combined crucible and sediment was then weighed, and placed
in a rack for ignition.

The samples were placed in a muffle furnace and ignited for 2 hours at
500 °C. They were then cooled in a desiccator to room temperature and
weighed. The difference (i.e. weight loss) between this weight (minus
the crucible weight) and the initial dry weight was the quantity of
total organic matter (TOM) in the sediment (Equation 1).

dry wt. sample - wt. after ignition at 500 °C = wt. total organic matter
(TOM) (1)

The percent by weight of TOM in the sediment was calculated using
Equation (2).

\\F(wt. TOM,dry wt.) 100 = % dry weight TOM (2)

The samples were then returned to the muffle furnace, ignited for one
hour at 1000 °C, cooled in a desiccator to room temperature and weighed.
The weight loss between 500 °C and 1000 °C was the amount of carbon
dioxide (C02) evolved from the carbonate minerals in the samples. The
weight of CO2 evolved was converted to percent carbonate material by the
following equations (3 - 5):

wt. after 500 °C - wt. after 100O °C = wt. CO2 evolved (3)

\\F(wt. C02,0.44) = wt. carbonate material (4)

where 0.44 is the atomic ratio of CO2 in CaCO3.

\\F(wt. CaC03,dry wt. sample) 100 = % dry wt. CaCO3 (5)

Ten percent of each sample run were full procedural blanks. The blanks
showed no weight changes during either the organic or the carbonate
ignition procedure.

Twelve percent of the samples were run as replicates, to establish the
precision of the method. The replicates were chosen to include samples
of high and low percentages of both organic

matter and carbonate content. The organic matter ignitions had a mean
variation of 0.3 percent with a standard deviation of 0.48. The
carbonate ignitions had a mean variation of 2.1 percent and a standard
deviation of 2.1.

Hirota and Szyper (1975) have shown that sediments with high (\>50%)
percentage of calcium carbonate can interfere with the accuracy of the
organic measurements. The interference results from carbonate CO2
evolution during the organic ignition (500 °C). For this reason a sample
of pure CaC03 was run with every set of samples to determine the maximum
limits of influence of CaC03 on organic matter (as Hirota and Szyper
suggest).

Only 0.03 percent of the CaCO3 standard was measured as organic carbon.
However, no sample containing greater than 50% CaC03 had an organic
content less than 1%; most containing greater than 2% TOM. Thus, the
natural proportions of TOM and carbonate found in the sediments analyzed
reduce the significance of this problem.

.c2.2.4. Hydrocarbon Analysis

.c3.2.4.1. Sediment

The methods used for the extraction of hydrocarbons were similar to
those previously described (Blumer *et al.*, 1969; Farrington *et al.*,
1972; and Sleeter *et al.* 1974). Wet sediment (25 - 75 g) was weighed
into cellulose thimble pre extracted with 1:1 benzene 0.5 N methanolic
KOH solution. Five grams of sample were weighed onto a watch glass and
placed in an oven at 105 °C for 3 hours for dry weight determination.
Sediments were extracted and saponified by refluxing for 48 hours with
the 1:1 benzene:0.5 N methanolic KOH solution. A plug of clean, light
copper turnings was placed beneath the cellulose thimble to remove the
elemental sulfur from the sample. A 0.5 mL volume of androstane and
*o*-terphenyl (1 mg/mL) was added to each sample as an internal
standard. Blanks were run with each set of 6 samples.

After 48 hours, the solution containing the extracted hydrocarbons was
removed from the Soxhlet and poured into a 500 mL separatory funnel. Any
residue left in the round bottom flask was washed with three small
aliquots of hexane and these washings were added to the extract.

Three successive 50-mL volumes of hexane were shaken vigorously with the
extracted methanol:benzene mixture, separating the aqueous and organic
layer, the three successive hexane:benzene mixtures were then combined
and the methanol aqueous phase was discarded.

The hexane-benzene mixture was washed first with organic free water
(prepared by passing distilled water through a large XAD-2 resin column)
and then with a saturated sodium chloride solution to remove trace
amounts of methanolic KOH. The combined extracts were dried over 1 g of
anhydrous sodium sulfate to remove residual water. The methanol and
water was discarded. The extract was concentrated to 5 mL in a
Kuderna-Danish apparatus using a water bath. The benzene-hexane
concentrate was transferred into a 12-mL evaporator tube, then the
concentrate was dried in a block heater under a stream of pure nitrogen
gas. The dry sample was then diluted to 1 mL with hexane, placed in a 5
mL vial with a foil-lined screw top and stored under refrigeration at 4
°C.

An alumina-silica gel column was pre-wet with 12 mL of hexane and the
sample was transferred onto a (10 x 1 cm) column packed with 1.25 cm of
alumina over 2.5 cm of silica gel. Both the alumina and silica gels had
been partially deactivated with 2% organic free water prior to packing.
The aliphatic fraction (f1) was eluted with 12 mL of hexane and a
similar volume of benzene was used to remove the aromatic fraction from
the column. Care was taken not to allow the hexane level to go below the
alumina layer during aliphatic elution. The aliphatic

fraction was reduced to 1 mL on a block heater under stream of pure
nitrogen gas, while the aromatic fraction (f2) was brought to almost
dryness and then diluted to 1 mL. The resultant samples were then stored
in a refrigerator at 4 °C until they were analyzed by gas
chromatography.

.c3.2.4.2. Tissue

The procedure for tissue analysis was similar to those described for the
sediment and consisted essentially of saponification, separation into
aliphatic and aromatic fractions and quantitative determination.
However, in the case of tissue there was a slight change in the
procedure for Soxhlet extraction as ethanolic KOH was used instead of
1:1 benzene: methanolic KOH. This reduced the possibility of ester
formation.

The above procedure was used for tissue extraction during the first year
study, however, it was found that more complete and faster extraction
could be attained by placing the homogenized tissue in a round bottom
flask, adding 150 mL of ethanolic KOH and extracting it for four hours
under a reflux condenser. Thus, this procedure was used in the second
year study. After the extraction, the mixture was poured into a
separatory funnel and was extracted three times successively with 100 mL
and two 50 mL portions of hexane. The alcoholic phase was then
discarded, and the combined hexane extracts were washed free of caustic
with organic free water and finally with saturated sodium chloride
solution. The hexane extract was then poured from the separatory into an
Erlenmeyer flask containing anhydrous sodium sulfate.

After drying the hexane extract was concentrated, separated into
aliphatic (f1) and aromatic (f2) fractions on an alumina-silica gel
column and again concentrated for gas chromatographic analysis as
described previously.

The tissue sample was homogenized prior to extraction and copper was not
necessary to remove sulfur from the tissue sample.

.c3.2.4.3. Water

In the laboratory, the 19-liter water samples were placed in a wooden
frame over a large magnetic stirrer. The water sample was unsealed and
the volume of each was adjusted to exactly 18 liters by siphoning down
to the mark. The 100 µL volume of androstane and *o*-terphenyl (1 mg/mL)
was added to each water sample as an internal standard. Then a large
egg-shaped spin bar and 500 mL of methylene chloride was added to each
sample; the magnetic stirrer was turned on and the speed adjusted to
give a deep vortex for good mixing.

After extracting in this manner for 24 hours, a glass siphon was
inserted in each sample and the methylene chloride extract was drawn
from the bottom of the water bottle into a separatory funnel. Then the
siphon was raised and the water was drawn down. The siphon was then
removed and the remaining water and methylene chloride poured into the
separatory funnel.

The methylene chloride extract was separated from the water, dried over
anhydrous sodium sulfate, and evaporated down in a Kuderna-Danish
concentrator. The sample was picked up in hexane, separated from
aliphatic (f1) and aromatic (f2) fractions on an alumina-silica gel
column, concentrated on a block heater, and placed in vials by the same
procedure as used for sediments.

.c3.2.4.4. Gas Chromatographic Analysis

A 1.0 to 2.0 µL volume of the concentrate was injected into a Tracor
model 563 gas chromatograph. This gas chromatograph was equipped with
dual flame ionization detectors and two fused quartz capillary columns.
In the first year\'s program, a 15-m SE 54 and a 25-m SE 30 column were
used for the determination of the aromatic and aliphatic compounds
respectively. These columns were replaced with two 30-m J & W columns
coated with SE 30 for better resolution in the second year\'s work.
Hydrogen was used as the carrier gas and a flow of 30 mL/min. was
maintained. For the first year\'s study, the chromatograph was set to
maintain the injector and detector temperatures at 280 °C and the oven
temperature was programmed from 60 °C to 300 °C at a rate of 1O °C/min
after an initial hold of 2 minutes and a final hold of 300 °C for 10
minutes. The temperature programming was changed slightly for the second
year\'s study and, in general, the injector and detector temperatures
were maintained at 300 °C and the chromatograph was programmed for oven
temperatures of 100 °C to 300 °C at 8 °C/min with no initial hold and a
final hold of 5 minutes. A full description of conditions is shown in
Table 2. All samples were injected in the splitless mode. Two
Hewlett-Packard integrators model 3390A were programmed to record the
retention time, areas under the peaks and to calculate the amounts of
hydrocarbons from C12-C3O. The integrators were calibrated with a
standard mixture. The aliphatic mixture contained hydrocarbons from C12
through C3O including phytane, pristane and androstane. The calibration
mixture used for the aromatics had naphthalene, phenanthrene,
dibenzothiophene and pyrene as well as the internal standards
*o*-terphenyl, 1-methylphenanthrene was added in the second year\'s
study. The standard mixtures were run daily and the integrators were re
calibrated as necessary.

The quantification of the chromatograms involved evaluating the known
and unknown peaks, the internal standards and the unresolved complex
mixture for their retention times and areas. Calibration mixtures were
run to determine response factors (concentration injected divided by the
area of peak). The integrators were programmed with time windows to
detect all reference peaks in the C12 to C3O range and label them. In
addition, it determined the area for all other peaks. The response
factors for the internal standards, androstane for the aliphatics and
*o*-terphenyl for the aromatics, were used to quantify the concentration
of all unknown peaks and the unresolved complex mixture.

The intergrators were capable of integrating under only one set of
parameters, therefore the unresolved complex mixture was quantified
separately. This involved tracing the unresolved area on a sheet of
paper, cutting it out, determining its area and correcting to units
which were comparable to the other data generated by the integrator. The
areas of the unresolved tracings were determined by a Hayashi Denko,
Type AAM-5 Automatic Area Meter. This unit is a photoelectronic
apparatus that automatically determines the area of any opaque or
semitransparent material by the amount of light it reflects. The area
was reported in cm2 by the area meter, and converted to integrator units
by a conversion factor. This information, the areas for the known and
unknown peaks, the response factors, sample number, dry weight, volume
injected, and final dilution volume were all entered into a computer
program written to calculate and quantify this data. The program
calculated the µg/g concentration for all of the reference peaks,
resolved (includes reference peaks and resolved unknown peaks), and
unresolved (unresolved complex mixture) areas, total hydrocarbons, the
carbon preference index (CPI), the percent recovery, and the following
ratios; resolved/unresolved, pristane/phytane, C17/pristane, and
C18/phytane. In the year-one program those samples that did not contain
the internal standards were corrected to a standardized recovery.

.c8.Table 2. Gas chromatograph operating conditions for the second year
study.

Descriptor Column 1 Column 2

Column Type SE-30 SE-30

Column length (m) 30 30

Column velocity (cm/sec) 41.7 41.4

Detector gases

H2 (cc/min) 30 30

Air (SCHF) 1.0 1.0

Injection timer (sec) 30.5 30.5

Detector temperature (°C) 300 300

Injection port temperature (°C) 300 300

Temperature Program

Initial temperature 100 °C

Final temperature 300 °C

Program rate 8 °C/min

Initial hold 0 min

Final hold 5 min

.c2.2.5. Radiocarbon Dating

To ensure the absence of any contamination during collection,
transportation, subsampling, storage and analysis, sediment collected at
a depth of 2 to 4 m were analyzed for hydrocarbons and 14C dated to
ensure that they were pre anthropogenic. Ten samples representing both
peat and shell substrates were collected. The samples were dated by the
University of Miami, Beta Analytic, Inc. Sampling, storage, subsampling,
and analysis followed the same procedures as all other sediment samples.

.c2.2.6. Computer Mapping

A computer program was used to graphically depict the spatially
distributed information generated by this project and assist in its
interpretation. The program, titled SYMAP, was developed by the
laboratory for Computer Graphics and Spatial Analysis, Harvard Center
for Environmental Design Studies, Graduate School of Design, Harvard
University, Cambridge, MA. The package assigns values to the coordinate
locations of data points or data zones, and can generate three basic
types of maps; contour, proximal and conformant. For this study only the
contour program was used. This program uses values assigned to a set of
coordinate locations and interpolates between data points assuming a
continuous variation exists between these points.

.c1.3. Intercalibration

Interlaboratory calibration exercises were carried out in the three
laboratories (Mote Marine Laboratory, Jacksonville University and
University of Miami) involved in hydrocarbon analysis during both years
of the study. These exercises were undertaken to ensure the
compatibility of results from all laboratories. Table 3 lists the
samples exchanged during the two-year study.

Only the results from the offshore sediment samples are reported since
all other intercalibration exercises have been completed and reviewed.
Tables 4 and 5 presents the concentrations of the aliphatic and aromatic
hydrocarbons and their key characteristics. Appendix F and G contains a
more detailed report of the analyses. Figures 4, 5 and 6 show the
chromatograms for the aliphatic fraction. As can be seen from the tables
all of the samples contained very small amounts of hydrocarbons. This is
what would be expected from a sample collected in non contaminated
offshore environment. The only sample which showed any unusual
characteristics was the Jetties sample collected by Jacksonville
University. This sample contained a small UCM and had a homologous
series from C15-C30.

.c1.4. Results and Discussion

.c2.4.1. Grain Size Analysis

Table 6 presents the distribution of grain sizes for the surface
sediments. The data is reported on a percent dry weight basis for three
size classes; gravel (\>2000 µ), sand 2000 µ - \>63 µ) and silt-clay
(\<63 µ).

The distribution of the gravel fraction ranged from 0 to 66 percent. The
mean was 7.9 percent with a standard deviation of 11.19. Figure 7 is a
histogram showing the distribution of samples analyzed. Sixty-eight
percent of the samples were composed of 10 percent or less of gravel.
The samples which contained high quantities of gravel were almost always
associated with areas where spoil had been deposited or dredging had
taken place. The percentage of sand in the sediments ranged from 1.3
percent to 98.4 percent. The mean value for the samples collected was
62.9 percent and the standard deviation was 25.00. Figure 8 is a
histogram of the distribution of sand in the surface sediments. The
majority of the samples contained in excess of 20 percent sand. The
quantity of sand in the samples collected from the northern areas of the
Bay showed a large variation which is most likely due to extensive
dredging activities. The silt-clay fraction ranged from 0.6 to 98.7
percent. The mean was 29.18 percent and the standard deviation was
25.70. The silt-clay fraction accounted for less than 40 percent in most
of the samples. The distribution for the silt-clay fraction is shown in
Figure 9. There were 9 samples in which the silt-clay fraction exceeded
80 percent. These samples were distributed throughout the Bay. Several
were associated with canal bottoms and dredge holes and two of the
samples were collected from Featherbed Bank.

.c2.4.2. Organic and Carbonate Content

Table 7 presents the results of the organic matter and carbonate
analyses of the surface sediments. Figures 10 and 11 are histograms of
the organic matter and carbonate content of the sediments, respectively.
The organic matter ranged from 0.17 percent to 33.22 percent. The mean
value was 5.1 percent and the standard deviation was 5.10. The majority
of the samples had organic contents of less than 8 percent. The samples
with high organic matter content (\>10%) were predominantly located in
the southern areas of the Bay and usually associated with canal bottoms.
Canals sampled in the northern areas of the Bay contained high

.c8.Table 3. Summary of intercalibration samples for the two-year study.

Originator Sample

First Year

> Mote Marine Laboratory South Louisiana Crude Oil
>
> Sediment spiked with Kuwait Crude Oil
>
> Tissue spiked with Kuwait Crude Oil
>
> Oyster
>
> Trout
>
> Mullet
>
> Jacksonville University Oyster
>
> Crab
>
> Sea Trout
>
> University of Miami Mullet spiked with #2 Fuel Oil

Second Year

> NOAA Duwamish Sediment
>
> Mote Marine Laboratory D-1
>
> D-2
>
> D-3
>
> Jacksonville University Jetties
>
> Atlantic Beach
>
> N6A
>
> University of Miami 201
>
> 202
>
> 203

.c8.Table 4. Aliphatic hydrocarbon characterization of interlaboratory
sediment samples collected during Year 02. All values are corrected for
percent recovery and expressed on a dry weight bases.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory/ f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

Sample (µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

University of Miami

201 1.08 (0.76) 2.6 ND 0.28 0.66 0.53 TD 0.02 0.09 ND C17-C28 2.53

202 0.83 (0.90) 0.8 ND ND ND ND ND ND ND ND ND ND

203 3.94 (0.02) 7.1 ND ND ND ND ND ND ND ND ND 1.7

Mote Marine Laboratory

D-1 3.19 (0.44) 2.2 ND 0.23 1.77 0.18 ND 0.03 1.44 0.12 C17-C29 1.35

D-2 2.57 (0.35) 1.9 ND ND 0.34 0.73 TD 0.02 1.52 ND C12-C25 1.30

D-3 2.50 (0.90) 2.0 ND 0.85 1.27 0.23 ND 0.01 1.22 ND C17-C30 0.61

Jacksonville University

Jetties 5.40 (0.45) 3.3 1.65 1.63 0.91 0.59 0.01 0.02 0.12 0.77 C15-C30
3.49

Atlantic 6.30 (4.06) 8.3 ND ND ND 1.33 0.08 ND 0.07 ND C15-C27 2.07

Beach

N6A 0.72 (0.50) 0.3 ND ND ND ND ND ND ND ND ND ND

\* Mean and standard deviation of three replicates.

ND = None Detected

TD - Trace Detected

.c8.Table 5. Aromatic hydrocarbon characterization of interlaboratory
sediment samples collected during year 02. All values corrected for
percent recovery and expressed on a dry weight bases.

Laboratory/ Total f2 Naphthalene Dibenzo- Phenan- 1-Methyl- Pyrene

Sample (µg/g) thiophene threne phenanthrene

University of Miami

202 1.05 (1.01) ND ND 0.01 0.04 ND

203 0.55 (0.43) ND 0.07 ND ND 0.03

Mote Marine Laboratory

D-1 1.42 (1.42) ND 0.04 0.04 0.03 0.04

D-2 1.35 (0.91) ND 0.03 0.03 0.05 0.02

D-3 1.22 (1.35) ND 0.02 0.04 0.05 0.06

Jacksonville University

Jetties 1.65 (1.10) ND 0.09 0.02 0.08 0.26

Atlantic Beach 0.76 ND ND ND ND ND

N6G 2.47 (2.08) ND ND 0.03 0.04 0.06

\* Mean and standard deviation of three replicates.

ND - None Detected

![](media/image9.pct){width="5.222222222222222in"
height="8.222222222222221in"}

.c7.Figure 4. Chromatograms of aliphatic (f1) fraction. Interlaboratory
calibration - offshore sediment samples - University of Miami.

![](media/image10.pct){width="5.027777777777778in"
height="7.944444444444445in"}

.c7.Figure 5. Chromatograms of aliphatic (f1) fraction. Interlaboratory
calibration - offshore sediment samples - Mote Marine Laboratory.

![](media/image11.pct){width="5.236111111111111in"
height="8.069444444444445in"}

.c7.Figure 6. Chromatograms of aliphatic (f1) fraction. Interlaboratory
calibration - offshore sediment samples - Jacksonville University. a)
Jetties samples, b) Atlantic Beach sample, c) sample N6A.

.c8.Table 6. Summary of surface sediment (0-5 cm depth) grain size
analysis. All values are percent dry weight.

Sample Gravel Sand SiltClay

\# (\>2000 µ) (2000 - 63 µ) (\<63 µ)

1 4.0 88.9 7.1

2 20.4 68.8 10.8

3 8.4 46.3 45.3

4 9.1 62.1 28.8

5 4.7 77.9 17.4

6 7.5 44.5 48.0

7 2.8 25.3 71.9

8 1.6 86.8 11.6

9 1.1 69.6 29.3

10 4.5 86.8 8.7

11 0.4 96.5 3.1

12 1.6 56.4 42.0

13 7.7 83.3 9.0

14 28.0 42.9 29.1

15 7.2 60.4 32.4

16 12.2 43.3 44.5

17 0.2 19.1 80.7

18 6.9 41.0 52.1

19 0.8 9.5 89.7

20 10.6 72.8 16.6

21 2.8 37.0 60.2

22 0.6 98.4 1.0

23 2.7 93.2 4.1

24 0.0 98.3 1.7

25 34.2 61.3 4.5

26 0.0 84.2 15.8

27 22.0 74.3 3.7

28 7.4 83.8 8.8

29 0.3 77.7 22.0

30 2.4 94.5 3.1

31 24.2 73.2 2.6

32 9.4 47.3 43.3

33 0.0 4.8 95.2

34 0.8 51.0 48.2

36 1.6 83.4 15.0

37 1.2 97.6 1.2

38 1.8 75.5 22.7

39 7.0 90.5 2.5

40 44.5 30.5 25.0

41 15.1 78.5 6.4

42 10.4 34.1 55.5

43 10.9 26.9 62.2

44 1.5 89.7 8.8

45 3.8 88.5 7.7

Table 6. Summary of surface sediment (0-5 cm depth) grain size analysis.
All values are percent dry weight (cont.).

Sample Gravel Sand SiltClay

\# (\>2000 µ) (2000 - 63 µ) (\<63 µ)

46 34.0 55.8 10.2

47 1.0 85.7 13.3

48 0.4 98.0 1.6

49 0.0 11.1 98.9

50 0.6 38.0 61.4

51 0.0 28.7 71.3

52 0.5 10.9 88.6

53 8.7 71.2 20.1

54 15.2 79.7 5.1

57 0.2 31.0 68.8

58 0.6 38.5 60.9

59 13.1 57.2 29.7

60 0.8 29.4 69.8

61 0.0 36.6 63.4

62 0.0 47.5 52.5

63 0.5 92.6 6.9

64 11.0 77.2 11.8

65 0.5 89.0 10.5

66 0.0 41.6 58.4

67 0.0 88.2 11.8

68 0.7 49.4 49.9

69 1.8 96.5 1.7

70 16.2 90.0 3.8

71 13.2 73.2 13.6

72 33.2 60.5 6.3

73 0.2 96.1 3.7

74 1.9 92.5 5.6

75 15.3 71.4 13.3

76 2.1 82.1 15.8

77 16.1 74.4 9.5

78 56.0 40.2 3.8

79 66.2 25.1 8.7

80 0.7 47.3 52.0

81 23.2 40.1 36.7

82 0.3 69.4 30.3

83 12.1 28.7 59.2

84 8.9 83.3 7.8

85 2.6 67.4 30.0

86 6.9 62.0 31.1

87 2.5 85.5 12.0

88 4.1 91.0 4.9

89 1.3 73.9 24.8

90 1.7 85.2 13.1

91 3.1 85.9 11.0

92 40.2 56.2 3.6

Table 6. Summary of surface sediment (0-5 cm depth) grain size analysis.
All values are percent dry weight (cont.).

Sample Gravel Sand SiltClay

\# (\>2000 µ) (2000 - 63 µ) (\<63 µ)

93 20.5 75.4 4.1

95 9.3 49.9 40.8

96 15.6 28.0 56.4

97 1.5 77.2 21.3

98 0.7 85.0 14.3

99 4.7 84.5 10.8

100 21.5 74.5 4.0

101 0.0 18.3 81.7

102 0.3 80.7 19.0

103 12.2 76.2 11.6

104 8.5 49.5 42.0

105 0.4 65.7 33.9

106 38.8 41.8 19.4

107 7.8 56.3 35.9

108 5.7 78.1 16.2

109 2.8 83.5 13.7

110 2.6 28.0 69.4

111 3.1 87.2 9.7

112 3.6 86.7 9.7

113 4.8 62.3 32.9

114 6.3 87.6 6.1

115 1.2 47.7 51.1

116 4.6 52.5 42.9

117 8.9 47.7 43.4

118 4.2 42.3 53.5

119 1.9 84.7 13.4

120 12.2 26.6 61.2

121 5.2 28.9 65.9

122 3.0 26.2 70.8

123 0.3 93.7 6.0

124 3.4 73.1 23.5

125 9.9 62.1 28.0

126 7.3 69.5 23.2

127 19.8 76.6 3.6

128 20.5 78.9 0.6

129 1.2 92.0 6.8

130 0.8 94.9 4.3

131 9.3 43.6 47.1

132 11.7 51.7 36.6

133 43.5 50.3 6.2

134 0.0 59.1 40.9

135 0.0 1.3 98.7

136 0.0 5.0 95.0

137 0.4 65.3 34.3

138 0.6 72.5 26.9

Table 6. Summary of surface sediment (0-5 cm depth) grain size analysis.
All values are percent dry weight (cont.).

Sample Gravel Sand SiltClay

\# (\>2000 µ) (2000 - 63 µ) (\<63 µ)

139 3.4 88.0 8.6

140 0.7 91.7 7.6

141 9.8 86.7 3.5

142 0.8 31.2 68.0

143 0.5 91.7 7.8

144 1.9 78.7 19.4

145 23.3 64.5 12.2

146 11.0 37.0 52.0

147 1.2 34.3 64.5

148 0.7 78.5 20.8

149 4.0 27.1 68.9

150 2.5 5.2 92.3

151 4.3 82.4 13.3

152 0.0 88.3 11.7

153 0.6 76.1 23.3

154 0.3 61.3 38.4

155 14.4 51.1 34.5

156 13.4 84.0 2.6

![](media/image12.pct){width="5.875in" height="4.555555555555555in"}

.c7.Figure 7. Histogram of percent gravel in surface sediments (0-5 cm).

![](media/image13.pct){width="5.944444444444445in"
height="4.541666666666667in"}

.c7.Figure 8. Histogram of percent sand in surface sediments (0-5 cm).

![](media/image14.pct){width="5.875in" height="4.583333333333333in"}

.c7.Figure 9. Histogram of percent silt-clay in surface sediments (0-5
cm).

.c8.Table 7. Summary of total organic matter and carbonate content of
surface sediments (0-5 cm depth).

Sample Organic Matter Carbonate (CaCO3)

(% Dry Weight) (% Dry Weight)

1 3.00 91.69

2 3.79 87.16

3 6.00 74.57

4 1.35 56.79

5 1.69 39.24

6 4.70 75.94

7 6.30 79.90

8 1.04 15.27

9 2.78 33.70

10 1.49 22.37

11 0.60 10.75

12 4.17 85.48

13 2.34 55.99

14 3.77 91.88

15 4.60 82.53

16 7.90 80.42

17 4.99 90.46

18 3.78 79.46

19 7.58 88.10

20 4.50 75.65

21 5.26 74.21

22 0.25 4.59

23 0.58 6.35

24 0.17 0.55

25 2.76 68.68

26 1.65 12.53

27 0.52 24.46

28 1.35 43.58

29 2.78 67.79

30 1.01 43.81

31 1.50 53.71

32 5.20 52.61

33 7.07 77.36

34 8.10 77.34

35 2.52 73.93

36 0.68 10.42

37 0.30 5.87

38 0.44 13.10

39 0.48 29.41

40 5.25 92.75

41 1.46 62.87

42 7.31 73.93

43 5.71 76.97

44 1.07 45.03

45 1.32 29.22

Table 7. Summary of total organic matter and carbonate content of
surface sediments (0-5 cm depth) (cont.).

Sample Organic Matter Carbonate (CaCO3)

(% Dry Weight) (% Dry Weight)

46 1.84 86.94

47 2.54 38.73

48 2.92 68.51

49 4.10 68.66

50 11.56 37.72

51 7.32 73.12

52 2.79 70.85

53 2.37 70.46

54 1.24 46.32

55 MD MD

56 MD MD

57 10.82 44.47

58 9.05 45.68

59 3.94 53.92

60 MD MD

61 9.50 47.18

62 7.47 56.61

63 1.70 11.74

64 3.13 12.92

65 1.70 5.47

66 13.45 45.37

67 0.34 1.95

68 12.66 41.30

69 0.86 7.68

70 0.98 30.04

71 2.35 93.80

72 2.61 44.31

73 0.68 1.87

74 0.77 12.99

75 11.54 18.73

76 2.06 54.39

77 1.43 52.35

78 1.15 87.67

79 1.59 89.88

80 4.35 69.50

81 4.37 81.80

82 13.94 5.32

83 7.36 87.01

84 2.41 77.72

85 3.43 39.75

86 3.75 70.20

87 3.83 80.03

88 2.74 85.72

89 2.11 32.23

90 1.27 20.27

Table 7. Summary of total organic matter and carbonate content of
surface sediments (0-5 cm depth) (cont.).

Sample Organic Matter Carbonate (CaCO3)

(% Dry Weight) (% Dry Weight)

91 2.12 46.80

92 23.06 48.13

93 2.89 54.16

94 MD MD

95 5.69 87.55

96 5.79 91.95

97 2.21 30.28

98 0.49 9.86

99 1.74 31.83

100 15.76 77.56

101 MD MD

102 15.93 66.01

103 17.49 67.77

104 7.12 80.14

105 7.60 86.91

106 7.69 88.20

107 17.56 71.48

108 1.98 40.39

109 2.39 28.95

110 11.20 77.09

111 2.39 57.01

112 14.47 68.06

113 4.54 44.51

114 2.30 59.30

115 6.95 58.32

116 5.54 90.67

117 5.51 87.24

118 15.16 78.97

119 1.42 13.62

120 MD MD

121 7.97 69.08

122 8.10 75.30

123 2.99 92.43

124 33.22 44.33

125 MD MD

126 5.58 53.06

127 MD MD

128 3.34 72.34

129 1.09 27.64

130 0.86 26.32

131 2.48 41.60

132 4.39 51.93

133 4.50 60.97

134 13.97 3.66

135 12.84 66.23

Table 7. Summary of total organic matter and carbonate content of
surface sediments (0-5 cm depth) (cont.).

Sample Organic Matter Carbonate (CaCO3)

(% Dry Weight) (% Dry Weight)

136 11.85 62.90

137 12.52 60.56

138 4.04 57.13

139 MD MD

140 2.59 47.03

141 1.45 44.70

142 9.92 68.20

143 1.75 53.80

144 2.93 57.36

145 3.12 53.60

146 21.29 41.95

147 6.72 63.77

148 3.53 20.08

149 7.80 52.79

150 MD MD

151 1.86 46.77

152 2.67 67.90

153 2.39 49.50

154 3.56 62.95

155 2.90 78.78

156 1.74 37.10

\* MD - Missing Data

![](media/image15.pct){width="5.944444444444445in"
height="4.541666666666667in"}

.c7.Figure 10. Histogram of percent organic matter in surface sediments
(0-5 cm).

![](media/image16.pct){width="5.944444444444445in"
height="4.541666666666667in"}

.c7.Figure 11. Histogram of percent carbonate material in surface
sediments (0-5 cm).

concentrations of organic matter also. The other samples which indicated
high organic content were collected from intertidal areas consisting of
a mangrove peat substrate. Carbonate content ranged from 0.6 to 93.8
percent. The mean of the samples collected was 53.3 percent with a
standard deviation of 26.12. Figure 11 shows that carbonate was
relatively evenly distributed throughout the samples collected. The
areas which exhibited the higher concentrations were distributed south
of Key Biscayne along the west side of the Bay.

.c2.4.3. Radiocarbon Dating

Figure 12 is a descriptive profile of the collected cores showing the
locations of the dated subsamples. Table 8 lists the location, sample
number, depth of subsample and age in 14C years. Table 9 and 10 lists
the aliphatic and aromatic hydrocarbon values and indices for the dated
samples. The dated material from cores 74, 78 and 152 showed that the
oldest material was in the surface layers. This would be expected since
all three of these cores were taken from spoil islands. The aliphatic
hydrocarbons concentrations were all low except for sample 152-p2.

.c2.4.4. GC-MS Analyses

Gas chromatography-mass spectroscopy (GC-MS) analyses was performed by
Dr. Edward S. Van Vleet, Associate Professor of Oceanography, Department
of Marine Science, University of South Florida. Samples were analyzed
using a Hewlett-Packard 5992B computerized GC-MS system equipped with a
30-m DB-5 fused silica capillary column. GC-MS system equipped with a
30-m DB-5 fused silica capillary column. GC-MS operating conditions were
as follows:

> Carrier gas: helium
>
> Column flow rate: 2 mL/min
>
> Injection port temperature: 240 °C
>
> Spitless injection mode
>
> Temperature program: 90-250 °C at 4 °C/min
>
> Electron multiplier voltage: 1200 or 1400 eV
>
> GC-MS run in selected ion monitoring mode
>
> Dwell time: 100 msec/ion

Specific ions monitored included C0-C3 naphthalenes, C0-C3 phenanthrenes
(plus anthracenes), C0-C3 pyrenes, C0-C2 benz\[*a*\]anthracenes and
dibenzothiophene. Standard polycyclic aromatic hydrocarbons (PAH)
mixtures were run each day for calculation of response factors.
Analytical uncertainty in the quantitative GC-MS determinations was
approximately ±30%. Interpretation relative to petrogenic versus
pyrogenic inputs was obtained by plotting the absolute abundance of the
PAH homologs. Fifteen samples, collected during the second year of the
study, were analyzed by GC-.MS. These included seven sediments, six
surface waters and two tissue samples. Table 11 lists the sample
numbers, type, location and results of the GC-MS analyses.

The water samples were essentially free of the aromatic hydrocarbons
that were monitored. Sample 227 contained peaks for C2-phenanthrene
although they were at the limits of sensitivity for the instrumentation
and are therefore questionable.

The two tissue samples did not show the normal range of PAHs expected
from simple petrogenic or pyrogenic inputs. These samples show only one
or two PAH components (C2- and/or C3-phenanthrenes in each case). The
PAH homologs in the oyster tissue are believed to be of petrogenic
origin. The catfish contained only one PAH component therefore its
source was uncertain.

![](media/image17.pct){width="5.819444444444445in"
height="8.902777777777779in"}

.c8.Table 8. Summary information for 14C dated sediment.

Midpoint Depth of

of dated sediment

University of interval surface

Miami below below Radiocarbon

Laboratory Collection Material sediment mean sea age

Core no. Sample no. Location dated surface level 14C years

  ------- --------- ------------------- ------ ---------- ------- -----------------
  72      UM-2670   North side of       peat   2.36 m     1.5 m   3370
                    Chicken Key Channel                           [+]{.underline}
                                                                  80

  ------- --------- ------------------- ------ ---------- ------- -----------------

  ------- --------- ------------------- ------- ---------- ------- -----------------
  74-p1   UM-2693   Spoil Bank 0.2 km   shell   3.40 m     1.1 m   4820
                    ESE from the mouth                             [+]{.underline}
                    of the Miami River                             90

  ------- --------- ------------------- ------- ---------- ------- -----------------

  ------- --------- ------------------- ------ ---------- ------- -----------------
  74-p2   UM-2672                       peat   3.70 m     1.1 m   4870
                                                                  [+]{.underline}
                                                                  90

  ------- --------- ------------------- ------ ---------- ------- -----------------

  ------- --------- ------------------- ------ ---------- ------- -----------------
  74-p3   UM-2667                       peat   4.00 m     1.1 m   3030
                                                                  [+]{.underline}
                                                                  120

  ------- --------- ------------------- ------ ---------- ------- -----------------

  ------- --------- ------------------- ------- ---------- ------- ----------
  78-p1   UM-2695   Spoil Island 0.7 km shell   2.10 m     0.8 m   4550 + 110
                    E of Biscayne Canal                            

  ------- --------- ------------------- ------- ---------- ------- ----------

  ------- --------- ------------------- ------- ---------- ------- -----------------
  78-p2   UM-2696                       shell   2.30 m     0.8 m   1950
                                                                   [+]{.underline}
                                                                   60

  ------- --------- ------------------- ------- ---------- ------- -----------------

  ------- --------- ------------------- ------- ---------- ------- -----------------
  80      UM-2694   2 km N from the NE  shell   3.40 m     1.8 m   3240
                    corner of the Julia                            [+]{.underline}
                    Tuttle Cswy.                                   125

  ------- --------- ------------------- ------- ---------- ------- -----------------

  ------- --------- ------------------- ------ ---------- ------- -----------------
  81      UM-2668   Central portion of  peat   2.95 m     1.6 m   5145
                    the *Halimeda* flat                           [+]{.underline}
                    between 79th St.                              110
                    and Julia Tuttle                              
                    Cswy.                                         

  ------- --------- ------------------- ------ ---------- ------- -----------------

  -------- --------- ------------------- ------ ---------- ------- -----------------
  152-p1   UM-2671   NE corner of Spoil  peat   2.10 m     1.5 m   4120
                     Island 1.3 km east                            [+]{.underline}
                     of Bakers Haulover                            80
                     Inlet                                         

  -------- --------- ------------------- ------ ---------- ------- -----------------

  -------- --------- ------------------- ------ ---------- ------- -----------------
  152-p2   UM-2669                       peat   2.50 m     1.5 m   3630
                                                                   [+]{.underline}
                                                                   80

  -------- --------- ------------------- ------ ---------- ------- -----------------

.c8.Table 9. Aliphatic hydrocarbon characterization of 14C dated
sediment samples. All values are corrected for percent recovery and
expressed on a dry weight bases.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory/ f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

Sample (µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

72 20.32 0.06 ND ND ND 4.77 ND 0.88 0.56 ND C17-C25 2.24

\(302\)

74-p1 3.92 0.04 ND ND ND ND ND ND 0.64 ND C17-C25 0.97

\(310\)

74-p2 7.12 0.04 ND ND ND ND ND ND ND ND ND ND

\(308\)

74-p3 ND ND ND ND ND NI) ND ND ND ND ND ND

\(305\)

78-p1 12.90 0.01 ND ND ND ND ND ND ND ND C16-C22 0.12

\(311\)

78-p2 3.21 0.15 ND ND ND ND ND ND 0.25 ND C12-C23 1.82

\(312\)

80 ND ND ND ND ND ND ND NI) ND ND ND ND

\(307\)

81 4.03 0.07 ND ND ND ND ND ND ND ND ND ND

\(306\)

152-p1 1.85 0.04 ND ND ND ND ND NI) 0.19 ND C18-C29 0.63

\(309\)

152-p2 216.84 6.51 0.08 0.23 ND 1.37 0.26 ND 0.58 ND C12-C23 0.89

\(301\)

ND - Not detected.

.c8.Table 10. Aromatic hydrocarbon characterization of 14C dated
sediment samples. Values are corrected for percent recovery and
expressed on a dry weight bases (µg/g).

Total

Sample f2 Napththalene Phenanthrene Dibenzothiophene Pyrene

72 (302) 35.01 ND 0.06 2.65 1.13

74-p1 (310) 8.67 ND 1.54 0.30 1.76

74-p2 (308) 19.31 ND 0.53 1.24 4.16

74-p3 (305) 0.83 ND ND ND ND

78-p1 (311) 10.80 ND 0.64 0.23 0.99

73-p2 (312) 2.08 ND 0.25 ND ND

80 (307) 0.59 ND ND ND ND

81 (306) 5.96 ND ND ND ND

152-p1 (309) 4.05 ND 0.35 0.11 1.17

152-p2 (301) 3.33 ND ND 0.12 0.82

\* ND = None Detected

.c8.Table 11. Summary of GC-MS characterization of PAH homologs.

Sample type Location Total GC-MS Major Probable Major

and number Aromatics (µg/g) Peaks\* Source

Water

208 Miami River 0.00 None None

210 Miami River 0.00 None None

227 Little River 0.11 C2P Uncertain

232 Goulds Canal 0.00 None None

238 Military Canal 0.00 None None

246 Black Creek 0.00 None None

Tissue

Catfish North Bay 0.4 C3P Uncertain

(*Arius felis*)

Flat tree oyster Marina 3.0 C3P, C2P Petrogenic

(*Isognomon alatus*)

Sediment

214 (0-5) Miami River 13.5 Py, C3Py Pyrogenic

214 (20-25) Miami River 3.9 Py, C3Py Mixed

225 (0-5) Little River 0.2 Py, P, C3P Pyrogenic

225 (55-60) Little River 0.2 C3P, C2P Petrogenic

232 (0-5) Goulds Canal 5.0 C3N, C3P Petrogenic

232 (55-60) Goulds Canal 13.2 C3N, C3P, Py Mixed

240 (0-5) Military Canal 0.5 C2P, C1P Petrogenic

\* N = Naphthalene; P = Phenanthrene; Py = Pyrene; C1, C2, C3 = homolog
number.

Sediments showed the best correlations of the three groups of samples
analyzed. Generally there was good agreement between the total PAHs
measured by GC and the PAHs measured by GC-MS. Figure 13 is a
scattergram of this data including the regression line. The correlation
coefficient (r) of this data is 0.87. This indicates that where high
concentrations of total aromatics were found by GC high concentrations
of the selected PAHs were also found by GC-MS. This is a good indication
that the aromatic fractions are derived from petrogenic or pyrogenic
sources. Sample 240 (0-5) appears to be anomalous. The GC-MS analysis of
this sample indicated values much lower than those obtained by GC. This
would indicate that most of the compounds in this sample are not PAHs.

In general, the correlation between the GC data and the GC-MS data was
good for total aromatics. The correlations for individual compounds was
poor. This poor correlation maybe explained by the misidentification by
GC of the selected compounds, naphthalene, dibenzothiophene,
phenanthrene, 1-methylphenanthrene and pyrene. GC-MS is generally
considered to be a more selective detector for these compounds. The
peaks identified by GC were either compounds that co-eluted or had very
similar retention times. These compounds are believed to be complex
pigments.

.c2.4.5. Hydrocarbon analysis and Distribution

Hydrocarbons in the marine environment are derived from three major
sources. These are biogenic, naturally occurring hydrocarbons produced
by terrestrial and marine organisms; pyrogenic, hydrocarbons generated
by forest fires and industrial combustion; and petrogenic, hydrocarbons
caused by petroleum contamination. These groups exhibit characteristic
patterns which make their identification possible. Although when in
combination these characteristics are diluted and positive
quantification becomes much more difficult.

A great deal of work has been devoted to the development of the criteria
for identification and separation of biogenic and petrogenic
hydrocarbons. One of the most widely used and accepted is to separate
the total extractable hydrocarbons into aliphatic (non-cyclic) and
aromatic (unsaturated) fractions. The methodology for this was discussed
previously. These fractions are then analyzed by GC-FID in conjunction
with packed and/or capillary columns. The use of GC- MS for the
quantification of the aromatic/olefinic fraction is of use in further
establishing the sources of the hydrocarbons.

Although both fractions are useful for the identification of petroleum
hydrocarbons the aliphatic has historically been used to a greater
extent. The indices developed for this fraction are numerous. Table 12
lists those characteristics used by this project for the interpretation
of the aliphatic chromatograms. These indices become somewhat ambiguous
when the sample contains both hydrocarbons of biogenic and petrogenic
origin. These mixtures obviously distort many of the indices.

The most reliable indicators found during this project were the
Unresolved Complex Mixture (UCM) and the HCC/TOM ratio. Biogenic
hydrocarbons in most sediments are few in number and simple in
structure, whereas for petroleum the opposite is true. Petroleum
compounds contain thousands of components, the majority of which are not
easily resolved by capillary column gas chromatography. These unresolved
compounds, when injected into a gas chromatograph, exhibit an inverted
saucer effect. This has been accepted by many as a vital characteristic
for the interpretation of gas chromatograms (NAS, 1975; Zafiriou, 1973;
Zafiriou *et al.*, 1972; Farrington and Medeiros, 1975). The other index
that proved very useful was the HCC/TOM ratio. This ratio is the total
hydrocarbons as carbon divided by the organic content of the sample. The
ratio was developed by Matsumoto (1982) for waters and modified by
Baddour

![](media/image18.pct){width="4.777777777777778in"
height="6.680555555555555in"}

.c7.Figure 13. Scattergram of total PAHs (f2) measured by GC vs. PAHs
measured by GC-MS.

.c8.Table 12. Criteria for distinguishing petrogenic from biogenic
hydrocarbons.

> CRITERION PETROGENIC BIOGENIC

+--------------------------+------------------+------------------------+
| 1\) Homologous Series    | Wide boiling     | Narrow boiling range   |
|                          | range (C1 to     | (C15 to C35)           |
|                          | C60)             |                        |
|                          |                  | Few series (2 or 3)    |
|                          | Several series   |                        |
+--------------------------+------------------+------------------------+

  --------------------------- ------------------- ------------------------
  2\) Odd-carbon predominance Absent (CPI         Usually present over a
                              [\~]{.underline} 1) narrow range (C15, C17
                                                  and/or C19 often
                                                  prominent)

  --------------------------- ------------------- ------------------------

  --------------------------- ------------------- ------------------------
  3\) Unresolved Complex      Present, often      Absent or barely
  Mixture (UCM)               dominant            detectable

  --------------------------- ------------------- ------------------------

  --------------------------- ------------------- ------------------------
  4\) Isoprenoid distribution Appreciable         Pristane often abundant,
                              pristane (C19),     no others detected
                              phytane (C20), C16, 
                              C18                 

  --------------------------- ------------------- ------------------------

  --------------------------- ------------------- ------------------------
  5\) Pristane/Phytane ratio  1.5 to 2.5          100 or greater

  --------------------------- ------------------- ------------------------

  --------------------------- ------------------- ------------------------
  6\) Resolved/Unresolved     1 but not zero      Infinite
  Complex Mixture (Res/UCM)                       

  --------------------------- ------------------- ------------------------

  --------------------------- ------------------- ------------------------
  7\) Total hydrocarbon as    Larger ratio        Smaller ratio
  carbon/total organic matter                     
  (HCC/TOM)                                       

  --------------------------- ------------------- ------------------------

\(1983\) and used for sediments. The original ratio HCC/TOC compared the
total hydrocarbon as carbon (total hydrocarbon content x 0.851, as
C20H42) to the total organic carbon content of the sample. Matsumoto
(1982) states that usually hydrocarbons are minor constituents in living
organisms, thus material contaminated with artificial hydrocarbons (e.g.
petroleum products) would have a much higher ratio than those containing
only natural hydrocarbons. Baddour modified the ratio by substituting
total organic matter for total organic carbon. His results show that
this ratio was quite reliable for the study of fuel spills around the
Miami International Airport.

Tables 13 and 14 present a summary of the aliphatic and aromatic
hydrocarbon content of the surface sediments collected during the first
year of the project. The hydrocarbon concentrations presented in these
tables have been corrected for percent recovery. Although only 22
percent of the samples analyzed during the first year contained internal
standards for calculation of percent recovery, a mean value of 28.3
percent with a standard deviation of 8.60 was obtained from these data
and used to correct all analyses. A more detailed listing of each sample
analysis is given in Appendices D and E.

.c8.Table 13. Aliphatic hydrocarbon characterization of surface
sediments collected during Year 01. All values are corrected for percent
recovery and are expressed on a dry weight basis.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

(µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

1 0.77 MD ND ND ND ND ND ND ND ND ND ND

2 2.41 0.5 ND ND 0.22 ND 0.16 0.01 1.18 ND C15-C25 ND

5 1.67 0.2 ND 2.97 0.07 0.57 0.04 0.02 0.06 ND C15-C25 2.33

6 22.53 1.0 0.37 0.51 2.33 2.43 0.08 0.20 1.23 ND C15-C25 1.58

7 33.23 6.1 0.45 0.67 0.21 0.51 0.34 0.01 0.13 ND C12-C25 1.74

8 1.77 0.1 ND 0.94 0.33 0.57 ND 0.01 0.94 ND C17-C25 9.98

9 0.05 0.1 ND ND ND ND ND ND 0.05 ND ND ND

10 1.76 0.5 ND ND ND ND ND ND 0.11 ND C15-C26 1.57

11 46.11 12.6 ND 73.39 ND 0.94 ND ND 3.84 ND C16-C25 2.57

12 71.99 23.9 0.36 6.28 1.06 3.42 ND 0.05 1.21 3.97 C17-C29 18.33

13 74.84 23.2 0.04 ND ND 0.70 0.08 0.40 ND ND C14-C23 ND

14 1.33 0.3 ND ND ND ND ND ND 0.14 ND ND ND

15 1.83 0.4 ND ND 0.55 ND 0.15 0.04 0.02 ND C15-C25 3.61

16 0.59 0.3 ND ND ND ND ND 0.26 ND ND ND 5.13

17 1.20 0.1 ND ND ND ND ND ND 0.02 ND C19-C25 1.68

18 0.09 0.9 ND ND ND ND ND ND ND ND ND ND

19 12.80 58.9 ND 3.02 0.02 3.90 0.14 0.01 1.19 ND C15-C25 0.99

20 6.35 2.4 ND ND ND ND ND ND 0.56 ND C21-C28 12.06

21 67.00 34.6 0.14 50.38 ND 0.81 0.06 ND 0.43 ND C15-C23 3.33

22 8.74 2.4 0.01 ND ND ND ND ND ND ND ND ND

23 70.22 8.8 0.02 2.68 ND 0.04 0.11 ND ND ND C15-C23 2.82

24 47.96 1.3 0.16 1.29 18.55 1.42 0.03 0.69 0.15 ND C15-C23 8.50

25 33.37 0.2 0.09 5.48 ND 1.12 0.03 ND 0.32 ND C14-C25 2.27

26 23.22 6.1 0.09 5.49 ND 1.12 0.03 ND 0.22 ND C12-C23 2.28

27 1.06 1.8 ND 5.54 ND 1.30 ND ND 0.14 ND C18-C22 2.16

28 0.12 0.2 ND ND ND ND ND ND 0.01 ND C21-C23 1.84

29 6.11 2.4 ND 0.21 3.22 2.35 ND 0.04 0.30 ND C17-C26 1.25

30 0.03 4.6 ND ND ND ND ND 0.03 ND ND ND ND

31 15.36 1.0 ND ND ND ND ND 0.03 0.06 ND C12-C25 0.76

32 102.45 21.3 0.50 1.73 0.32 1.35 0.07 0.03 0.25 12.21 C12-C29 4.30

33 10.88 1.1 ND ND ND 0.19 ND 0.89 2.30 ND C16-C26 4.96

34 31.60 21.3 0.02 ND ND 1.84 ND ND 0.17 ND C18-C23 2.46

35 0.42 0.2 ND 7.21 ND ND ND ND ND ND ND ND

36 11.24 2.5 0.03 ND ND ND ND ND 0.08 ND ND ND

38 2.83 2.2 ND ND ND ND ND ND ND ND ND ND

40 0.29 0.1 ND ND ND ND ND ND ND ND ND ND

Table 13. Aliphatic hydrocarbon characterization of surface sediments
collected during Year 01. All values are corrected for percent recovery
and are expressed on a dry weight basis. (cont.)

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

(µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

41 17.01 6.1 0.04 ND ND ND ND ND ND ND ND ND

42 4.49 9.1 ND ND ND ND 0.19 0.49 0.74 ND C12-C25 13.30

43 15.55 2.4 ND 8.25 0.41 ND ND 0.08 0.07 ND C14-C26 0.13

44 2.01 0.8 ND ND ND ND ND ND 0.04 ND C21-C23 15.36

45 33.13 7.4 0.11 0.34 5.47 0.26 0.01 0.08 0.16 ND C12-C25 1.87

46 4.51 4.0 ND 0.60 0.16 ND ND 0.02 0.09 ND C14-C21 0.77

47 58.92 52.8 0.06 0.97 0.18 ND ND 0.01 ND ND C17-C22 0.01

48 29.44 2.3 0.04 0.55 0.88 ND ND 0.01 0.08 ND C17-C22 1.48

49 24.13 4.7 ND 0.60 ND ND ND ND 0.05 ND C19-C26 1.92

51 53.46 2.7 0.08 16.60 ND ND 0.12 ND 0.21 ND C12-C24 2.21

52 14.74 3.8 0.08 ND ND ND ND ND 0.08 ND C21-C23 3.64

53 7.38 2.9 1.24 ND 6.53 ND ND 0.07 0.41 ND C17-C23 12.77

54 1.34 0.2 ND 2.74 1.27 2.75 ND 0.04 0.08 ND C17-C23 1.82

55 0.25 1.1 ND ND ND ND ND ND 0.13 ND ND ND

56 280.82 0.6 0.04 0.01 153.98 0.43 0.10 1.44 0.05 ND C13-C24 2.68

57 669.96 7.9 0.03 0.06 5.93 0.54 0.02 0.27 0.19 ND C12-C24 1.07

58 187.43 0.4 0.04 6.33 0.14 0.51 0.14 0.07 ND ND C14-C21 1.58

59 913.55 8.1 0.04 1.47 0.13 0.66 0.27 0.17 2.82 ND C15-C24 1.77

60 1028.79 2.4 0.03 1.92 0.08 0.83 1.11 0.10 0.47 ND C12-C22 1.74

61 2449.60 11.4 0.02 9.93 ND ND 0.22 ND ND ND ND 0.21

62 185.54 3.4 0.01 ND ND ND 0.03 ND ND ND ND 2.36

63 0.39 0.2 ND ND ND ND ND ND 0.08 ND ND ND

64 76.98 63.3 ND 0.18 1.46 ND 0.09 0.01 0.10 ND C15-C27 7.12

65 0.52 3.9 ND 0.22 0.93 ND ND 0.01 0.06 ND C17-C21 ND

66 89.18 5.3 0.13 ND ND ND 0.25 ND 0.75 ND C15-C25 2.60

67 0.65 1.2 ND 1.04 ND 0.57 0.06 ND ND ND C15-C20 1.39

68 19.64 5.7 0.52 2.09 0.97 3.41 0.21 0.12 0.55 ND C15-C25 1.79

69 13.47 2.1 0.04 ND ND ND 0.01 ND 0.08 ND C15-C23 2.93

70 2.12 4.5 ND 0.97 0.18 0.18 0.14 0.02 0.04 ND C12-C23 1.39

71 5.21 MD ND ND ND ND 0.24 0.03 ND ND C12-C22 1.76

72 100.98 13.2 ND ND 0.27 ND ND 0.04 0.10 ND C17-C28 5.49

73 0.33 0.5 ND ND 2.43 ND 0.03 0.07 0.02 ND C15-C24 5.23

74 1.08 1.2 ND ND ND ND ND ND 0.08 ND ND ND

75 333.86 4.5 0.01 38.40 ND ND 0.30 ND ND ND ND 6.79

76 4.69 9.6 ND ND ND ND 0.18 ND 0.27 ND C15-C27 ND

77 74.70 0.1 0.09 0.57 1.22 0.85 0.10 0.39 0.10 0.39 C12-C29 4.84

78 ND ND ND ND ND ND ND ND ND ND ND ND

79 2.27 1.2 ND ND 0.53 ND 0.04 0.24 0.09 ND C15-C21 1.72

80 149.67 25.0 0.25 ND ND 0.83 ND 0.22 0.53 ND C17-C28 3.57

Table 13. Aliphatic hydrocarbon characterization of surface sediments
collected during Year 01. All values are corrected for percent recovery
and are expressed on a dry weight basis. (cont.)

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

(µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

81 7.01 3.4 ND ND ND ND ND ND 0.12 ND C21-C25 3.18

82 52.17 3.4 ND ND ND ND 0.19 ND 0.56 11.19 C15-C29 7.12

83 5.03 2.1 ND 1.31 ND 0.95 ND ND 0.16 ND C12-C25 1.30

84 103.30 22.4 0.20 2.64 ND ND 0.60 ND 1.18 ND C12-C24 1.93

86 4.45 3.8 ND 0.35 1.40 1.86 0.22 0.01 0.37 ND C12-C25 1.61

87 175.16 162.0 0.07 3.81 ND 0.61 ND ND ND ND C18-C26 2.16

88 0.76 0.1 ND ND ND ND ND ND 0.04 ND ND 0.62

89 0.22 1.7 ND ND ND ND 0.05 0.00 0.01 ND C12-C22 1.64

90 3.52 1.2 ND 34.12 ND 1.66 0.11 ND 0.48 ND C12-C25 4.03

92 1.47 9.2 ND ND ND ND ND ND 0.37 ND C21-C23 2.91

93 14.68 3.2 ND ND 1.56 ND 0.57 0.40 0.03 ND C12-C26 1.33

94 1.55 0.8 ND ND ND ND ND 0.01 ND ND C12-C20 1.05

95 5.82 0.4 ND ND 1.28 ND 0.17 0.13 0.18 ND C12-C21 1.50

96 55.11 1.9 0.15 0.54 ND 1.61 0.34 ND 0.47 ND C12-C25 1.54

97 5.18 0.2 ND ND ND ND 0.16 ND 0.21 ND C12-C21 4.23

99 13.03 592.8 ND ND ND ND 0.11 ND ND ND C12-C21 ND

100 5.82 0.2 ND ND 11.82 ND 0.07 1.33 0.73 ND C14-C25 7.39

101 204.53 19.0 0.12 0.14 88.40 1.07 0.04 3.59 0.40 ND C12-C27 3.28

102 98.30 18.5 0.22 54.43 ND 0.53 ND ND 0.32 ND C12-C25 2.90

103 777.12 121.9 0.10 3.38 2.57 0.12 0.34 6.40 1.41 ND C15-C25 9.79

104 ND ND ND ND ND ND ND ND ND ND ND ND

105 50.50 18.4 ND 75.69 ND 0.60 0.07 ND 0.25 ND C12-C28 1.64

106 1.07 0.2 ND ND 0.15 ND 0.08 0.01 0.01 ND C12-C24 0.93

107 6.38 6.0 ND ND ND ND ND ND ND ND ND ND

108 2.96 0.1 ND ND ND ND ND ND ND 1.47 C19-C24 ND

109 8.03 2.6 ND 13.60 0.12 5.64 0.06 0.13 0.11 ND C12-C25 0.86

110 5.01 0.4 ND ND ND ND ND 2.38 0.58 ND ND ND

111 4.45 23.3 ND ND 0.09 ND 0.25 0.04 0.58 ND C15-C21 ND

112 4.57 3.0 ND ND 1.16 ND ND 0.76 0.22 ND C12-C23 5.73

113 1.71 0.3 ND ND ND ND ND 0.11 0.18 ND C17-C25 12.10

114 0.75 0.2 ND ND 1.72 ND 0.07 0.08 ND ND C15-C19 1.95

115 2.63 2.8 ND ND ND ND ND ND 0.21 ND ND 0.41

116 4.34 0.7 ND ND ND ND 0.20 ND ND ND C12-C22 0.62

117 2.58 0.4 ND ND ND ND ND ND 0.02 ND ND 0.42

118 37.86 MD ND 5.31 ND ND ND ND 0.40 ND C19-C23 2.47

119 4.36 2.5 ND 2.15 23.09 ND ND 0.70 1.48 ND C17-C23 29.32

120 19.29 1.9 ND ND ND 1.76 0.04 7.25 0.86 ND C13-C25 8.44

Table 13. Aliphatic hydrocarbon characterization of surface sediments
collected during Year 01. All values are corrected for percent recovery
and are expressed on a dry weight basis. (cont.)

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

(µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

121 52.00 11.4 ND 274.03 ND 3.29 0.54 ND 0.15 13.06 C12-C29 2.42

122 62.94 MD ND 12.95 0.02 ND 0.02 0.02 0.37 22.19 C12-C29 3.92

123 0.73 0.1 ND ND ND ND 0.06 0.05 0.02 ND C15-C24 1.31

124 12.61 1.5 ND ND 3.95 ND ND 0.70 0.03 ND C17- C27 0.76

125 49.57 21.4 0.22 0.17 15.49 1.71 0.10 0.38 0.04 ND C12-C26 0.90

126 0.92 0.3 ND ND ND ND ND ND 0.39 ND ND ND

127 1.16 0.2 ND 11.73 ND 2.26 0.09 ND 0.10 ND C15-C23 2.46

128 34.90 260.6 0.34 ND ND 2.15 0.03 2.67 1.32 ND C15-C25 13.02

129 0.01 0.1 ND ND ND ND ND ND 0.01 ND ND ND

130 0.23 1.2 ND ND ND ND ND ND ND ND ND ND

132 4.66 0.2 ND 0.97 9.43 0.57 ND 0.77 0.45 1.42 C12-C29 4.24

134 43.16 2.5 0.30 ND ND ND 0.13 4.44 0.96 ND C12-C25 3.40

135 237.45 35.4 0.03 0.85 18.80 1.39 ND 0.96 0.70 ND C17-C25 9.92

136 484.47 31.3 0.03 ND ND 1.95 0.47 ND 0.66 ND C12-C25 2.64

137 28.79 5.4 0.01 ND ND ND ND ND 0.08 ND ND 2.21

138 24.50 ND 0.11 0.44 3.70 3.16 0.11 0.04 0.20 ND C15-C25 1.59

139 21.26 12.5 0.02 ND ND ND 0.03 ND 0.07 ND C15-C24 2.79

140 27.90 1.4 0.04 ND ND ND ND ND 0.31 ND C18-C23 5.01

142 308.74 54.4 0.04 ND ND ND 0.40 0.44 2.53 ND C15-C23 ND

143 1.09 0.3 ND ND 3.01 ND TD 0.01 0.03 ND C12-C23 0.97

144 73.07 15.6 0.03 1.03 0.31 7.97 ND 0.01 0.85 ND C17-C23 10.73

145 2.01 0.2 ND ND 5.43 ND 0.16 0.15 0.63 ND C12-C23 4.42

146 4.29 ND ND ND ND ND ND ND 0.23 ND C21-C26 0.57

147 216.69 43.3 0.08 ND ND ND ND ND 6.70 ND C18-C25 8.23

148 86.58 0.3 0.05 8.28 ND 0.38 0.02 ND 0.29 ND C15-C27 1.79

149 188.41 92.0 0.14 6.50 ND 1.16 0.26 ND 7.10 ND C12-C26 9.07

150 1.81 1.6 ND ND ND ND N ND 0.69 ND C18-C22 5.53

151 23.84 6.0 ND ND ND ND 0.01 0.05 1.04 ND C12-C23 1.36

152 81.21 102.3 0.08 ND ND ND 0.10 0.05 0.51 ND C15-C25 1.36

153 42.84 8.6 0.13 ND ND 10.01 0.13 ND 0.40 ND C14-C22 1.15

154 0.65 1.3 ND ND ND ND ND 0.19 0.17 ND C17-C21 12.91

155 86.19 MD 0.19 0.76 3.35 2.10 0.13 0.38 0.87 ND C12-C24 1.20

MD - Missing Data

ND - None Detected.

TD - Trace Detected

.c8.Table 14. Aromatic hydrocarbon characterization of surface sediments
collected during Year 01. Values are corrected for percent recovery and
are expressed on a dry weight basis.

Total

Sample f2 Napththalene Phenanthrene Dibenzothiophene Pyrene

1 MD

2 4.48 ND 0.03 0.17 0.27

5 8.92 ND 0.82 0.30 0.17

6 23.65 ND 0.02 0.09 0.06

7 5.42 ND 0.19 0.11 0.28

8 13.15 ND TD 0.17 0.04

9 2.45 ND 0.09 0.02 0.07

10 3.79 TD 0.04 0.13 0.07

11 3.67 ND 0.13 0.20 0.17

12 3.01 ND 0.11 0.19 0.01

13 3.21 ND 0.56 0.14 0.25

14 5.04 ND 0.10 0.23 0.63

15 4.10 ND 0.38 0.29 0.09

16 1.78 ND ND ND 0.36

17 24.94 0.07 1.00 0.18 6.30

18 5.62 0.06 1.21 0.07 0.01

19 14.29 ND 0.13 0.09 0.07

20 0.99 ND ND 0.05 ND

21 1.12 ND ND ND TD

22 3.58 ND 0.36 0.04 0.06

23 2.03 ND 0.40 0.10 0.10

24 MD

25 MD

26 3.81 ND 0.38 0.05 0.59

27 0.84 ND ND ND 0.10

28 0.71 ND ND ND ND

29 3.37 ND 0.33 0.06 0.76

30 0.67 ND 0.05 ND ND

31 6.28 ND 0.04 0.03 0.56

32 22.06 ND 0.02 0.46 0.73

33 10.46 0.14 0.05 0.32 0.78

34 1.48 ND 0.08 0.10 0.11

35 2.40 ND 0.24 0.18 0.37

36 4.51 0.26 0.08 ND 0.86

38 1.31 ND 0.03 0.06 0.23

40 22.98 0.08 0.12 2.05 ND

41 2.77 ND 0.02 0.40 0.03

42 0.49 0.06 ND ND 0.09

43 6.78 ND 0.08 0.05 0.28

44 2.44 ND ND ND 0.86

45 4.48 ND ND ND 1.47

46 1.71 ND 0.18 ND 0.14

47 1.12 ND 0.04 0.07 0.10

48 12.90 ND 0.07 ND 0.20

49 5.15 ND 0.62 ND 0.36

Table 14. Aromatic hydrocarbon characterization of surface sediments
collected during Year 01. Values are corrected for percent recovery and
are expressed on a dry weight basis. (cont).

Total

Sample f2 Napththalene Phenanthrene Dibenzothiophene Pyrene

51 19.72 ND 3.13 0.86 5.82

52 3.88 0.03 0.70 1.20 2.00

53 2.54 ND 0.73 0.23 0.08

54 5.67 ND 0.51 1.21 1.69

55 2.32 ND 0.02 0.02 0.80

56 459.15 ND 0.08 0.63 12.20

57 84.43 ND 0.14 0.35 3.15

58 420.84 ND 2.82 0.60 12.35

59 112.62 ND 0.26 0.63 ND

60 446.80 ND 1.26 4.51 33.73

61 213.85 ND 11.70 6.11 3.22

62 54.46 ND 0.14 1.34 7.32

63 20.87 ND 0.07 TD 0.83

64 1.22 ND 0.04 ND 0.44

65 0.13 ND ND ND ND

66 16.88 ND 0.18 0.56 5.73

67 0.57 ND ND 0.03 0.15

68 3.44 ND ND ND 0.16

69 6.40 ND 0.11 0.33 2.29

70 0.46 ND ND ND ND

71 MD

72 7.65 ND 0.28 ND 0.22

73 0.72 ND ND ND ND

74 0.87 ND 0.15 ND ND

75 43.54 ND 0.04 0.04 1.01

76 0.49 ND ND ND ND

77 10.06 0.03 0.65 0.06 3.73

78 9.49 ND 0.09 0.01 0.33

79 1.91 ND 0.18 ND 0.71

80 5.97 ND 0.04 ND 0.23

81 12.05 ND 0.05 0.12 2.90

82 15.20 0.10 0.18 0.73 4.42

83 2.40 ND ND 0.17 0.27

84 4.60 ND TD 0.44 0.60

86 1.16 ND ND ND ND

87 1.08 ND 0.06 ND 0.19

88 17.47 ND TD 0.51 0.79

89 0.13 ND ND ND ND

90 2.85 ND 0.01 ND 0.33

92 0.16 ND ND ND ND

93 4.63 ND 0.03 0.17 0.46

94 1.85 ND ND 0.02 0.21

95 13.14 ND 3.94 1.03 1.53

96 28.91 1.52 0.11 0.67 1.86

97 8.75 ND 0.10 0.02 0.27

Table 14. Aromatic hydrocarbon characterization of surface sediments
collected during Year 01. Values are corrected for percent recovery and
are expressed on a dry weight basis. (cont).

Total

Sample f2 Napththalene Phenanthrene Dibenzothiophene Pyrene

99 0.02 ND ND ND ND

100 24.29 ND 0.30 2.73 1.54

101 10.78 0.04 0.05 0.10 0.41

102 5.31 ND 1.04 0.53 0.28

103 6.37 ND 0.23 0.10 0.17

104 9.77 ND 0.03 0.10 0.28

105 2.74 ND ND 1.92 ND

106 4.99 ND 0.10 0.29 0.26

107 1.06 ND ND ND ND

108 245.33 ND 0.20 ND 0.25

109 3.41 ND 0.23 ND 0.62

110 12.75 0.20 0.04 0.22 0.83

111 0.19 ND ND ND ND

112 1.52 ND 0.04 0.14 0.13

113 5.63 ND 0.04 ND 0.10

114 4.26 ND 0.03 0.52 3.96

115 0.95 ND ND 0.03 ND

116 6.47 ND 0.02 0.16 1.81

117 7.33 ND 0.13 ND 1.69

118 MD

119 1.71 ND 0.09 1.01 ND

120 10.29 ND 0.28 0.61 ND

121 4.55 ND 0.08 0.24 0.62

122 MD

123 6.36 ND 0.07 0.13 0.60

124 8.50 ND 0.13 0.36 1.19

125 2.32 ND 0.22 ND 0.46

126 2.67 ND ND ND 0.08

127 5.11 ND 0.03 0.41 0.48

128 0.13 ND ND ND ND

129 0.23 ND ND ND ND

130 0.20 ND ND ND ND

132 18.93 ND 0.24 0.87 1.21

134 17.16 ND 0.06 0.22 0.26

135 6.70 0.08 0.17 0.18 1.04

136 15.48 0.33 0.21 0.21 0.89

137 5.34 ND 0.11 0.46 0.35

138 MD

139 1.70 0.04 0.04 0.05 0.16

140 20.05 ND 0.10 0.22 1.93

142 5.68 ND 0.22 0.26 0.94

143 4.09 ND 0.02 0.73 0.16

144 4.64 ND 0.41 0.04 0.66

145 9.42 ND 1.51 0.18 2.81

Table 14. Aromatic hydrocarbon characterization of surface sediments
collected during Year 01. Values are corrected for percent recovery and
are expressed on a dry weight basis. (cont).

Total

Sample f2 Napththalene Phenanthrene Dibenzothiophene Pyrene

147 5.00 ND 0.07 0.08 1.21

148 242.85 0.29 7.68 47.92 22.91

149 2.05 ND ND ND ND

150 1.15 ND ND ND 0.26

151 3.95 ND ND 0.10 1.72

152 0.79 ND ND ND ND

153 5.06 ND 0.04 0.03 0.05

154 0.50 ND ND ND 0.04

155 MD

> MD - Missing Data
>
> TD - Trace Detected
>
> ND - None Detected

Figures 14 and 15 show the distribution of aliphatic hydrocarbons and
the aromatic hydrocarbons. Several of the other indices were mapped
(CPI, C17/pristane, C18/phytane and the resolved/unresolved). The
mapping of these indices were of minimal use, added little to the
interpretation of the distribution of hydrocarbons, and because of the
high costs of reproducing them, are not presented.

To supplement the contour maps several of the indices were used to
separate those samples containing only biogenic material form samples
with petroleum contamination. It was found that the most useful index
for this was the HCC/TOM ratio in conjunction with the
resolved/unresolved (identifiable peaks/UCM) ratio. The HCC/TOM ratios
were ranked in ascending order and using the resolved /unresolved and
other indices (CPI, Pristane/Phytane, etc.) were separated into two
groups, those that showed indications of petrogenic hydrocarbons and
those that did not. Table 15 lists those samples, as per their location
and concentrations, containing petroleum contamination.

The data collected from these stations was then compared for
correlations using several regression equations. These included linear,
exponential, logarithmic and power law. Total, aliphatic and aromatic
hydrocarbons were compared to the three sediment grain sizes, organic
and carbonate content, water salinity and temperature. This exercise
showed no strong correlation between concentration of hydrocarbons and
any of the other parameters. The strongest correlation existed between
salinity and total hydrocarbons (correlation coefficient -0.54). Figure
16 presents a scattergram of the data and the regression line. Obviously
salinity has no effect on the distribution of hydrocarbons. This
relationship is a function of location to freshwater input.

Figures 14 and 15, and Table 15 indicate in general that many of the
samples which contained petroleum contamination were associated with
canals which receive runoff from large urbanized areas. This is further
supported by the inverse relationship of salinity (freshwater input) to
hydrocarbon content (the lower the salinity the higher the hydrocarbon
concentration) shown in Figure 16.

The highest concentrations of hydrocarbons were found in the sediments
of the Miami River. The highest concentration of aliphatics (2449.60
µg/g) was found at station 61, while the highest aromatic concentrations
(459.15 µg/g) were at station 56, near the railroad bridge located at
the most westerly point sampled.

Organisms were collected from several areas of the Bay and analyzed for
petroleum contamination. Table 16 and 17 lists these results. There were
no strong indication of contamination in any of the samples. Although
this maybe an artifact of the small sample size extracted.

The main purpose of the second year of the study was to investigate
areas where analyses indicated the presence of petroleum contamination.
Four primary and one secondary study areas were chosen. The primary
areas were: 1) the Little River; 2) the Miami River; 3) Black
Creek-Goulds Canal area; 4) Military Canal. The secondary area was
Snapper Creek. These areas were sampled for additional sediments,
surface water and biota if available.

The Little River and the Miami River are located in the northern part of
the Bay. The Little River is characterized by a residential community
near its mouth while its upper areas receive runoff from city streets.
The area is best characterized by inputs from urban runoff and a minimal
input from boat traffic. The projected changes within this area will
probably be minimal over the next several years. The Miami River
receives a great deal of boat and ship

![](media/image19.pct){width="3.5in" height="8.458333333333334in"}

.c7.Figure 14a. Distribution of aliphatic hydrocarbons (f1) in surface
sediments of Biscayne Bay. \[ORIGINAL\]

![](media/image20.pct){width="3.236111111111111in"
height="7.513888888888889in"}

.c7.Figure 14b. Distribution of aliphatic hydrocarbons (f1) in surface
sediments of Biscayne Bay. \[RECONSTRUCTION. HIGH VALUES UPSTREAM IN THE
MIAMI RIVER ARE NOT SHOWN. LOCATION OF LAND MASSES RELATIVE TO
HYDROCARBON DISTRIBUTIONS NOT CLEAR IN ORIGINAL.

![](media/image21.pct){width="3.4027777777777777in"
height="8.347222222222221in"}

.c7.Figure 15a. Distribution of aromatic hydrocarbons (f2) in surface
sediments of Biscayne Bay. \[ORIGINAL\]

![](media/image22.pct){width="3.1527777777777777in"
height="7.541666666666667in"}

.c7.Figure 15b. Distribution of aromatic hydrocarbons (f2) in surface
sediments of Biscayne Bay. \[RECONSTRUCTION. HIGH VALUES UPSTREAM IN THE
MIAMI RIVER ARE NOT SHOWN. LOCATION OF LAND MASSES RELATIVE TO
HYDROCARBON DISTRIBUTIONS NOT CLEAR IN ORIGINAL.\]

![](media/image23.pct){width="5.875in" height="4.208333333333333in"}

.c7.Figure 16. Scattergram of salinity vs. total hydrocarbons
(aliphatic + aromatic).

> .c8.Table 15. Surface sediment containing petroleum hydrocarbons
> collected during the first year of the study.
>
> Sample HCC/TOM Resolved/ Total Hydrocarbons Location
>
> (x 10-2) Unresolved (µg/g)
>
> Samples located north of Rickenbacker Causeway

32 1.06 0.50 124.51 Between San Marino and Hibiscus Islands

34 0.28 0.02 33.08 Belle Isle

36 0.13 0.03 15.75 Westend Venetian Causeway

45 0.32 0.11 37.62 Spoil Island

47 0.51 0.06 60.04 Intracoastal Waterway

48 0.36 0.04 42.34 Spoil Area

49 0.24 ND 29.28 Intracoastal Waterway

51 0.62 0.08 73.18 Canal mouth

56 MD 0.04 739.97 Miami River

57 6.42 0.03 754.39 Miami River

58 5.18 0.04 608.27 Miami River

59 8.73 0.04 1026.17 Miami River

60 MD 0.03 1465.60 Miami River

61 22.67 0.02 2663.45 Miami River

62 2.04 0.01 240.00 Miami River

75 3.21 0.01 377.41 Loading area - Belcher Oil

77 0.72 0.09 84.76 Canal mouth

80 1.32 ND 155.64 West end of Julia Tuttle Causeway

135 2.08 0.03 244.15 Dredged hole

136 4.25 0.03 499.95 Little River

137 0.29 0.01 34.14 Little River

138 MD 0.11 MD Normandy Waterway

142 2.67 0.04 314.42 Surprise Lake

144 0.66 0.03 77.71 Collins Canal

148 2.80 0.05 329.43 Junction of Royal Glades Canal and Oleta River

149 1.62 0.14 190.46 Maul Lake

153 0.41 0.13 47.90 Indian Creek

155 MD 0.19 MD Biscayne Point

> Table 15. Surface sediment containing petroleum hydrocarbons collected
> during the first year of the study (cont.).
>
> Sample HCC/TOM Resolved/ Total Hydrocarbons Location
>
> (x 10-2) Unresolved (µg/g)

Samples Located South of Rickenbacker Causeway

6 0.39 0.37 46.18 Intracoastal Waterway

7 0.33 0.45 38.65 Intracoastal Waterway

11 0.40 ND 47.78 East of Matheson Hammock

12 0.63 0.36 75.00 Safety Valve

13 0.67 0.04 78.06 Soldier Key

21 0.58 0.14 68.12 Northwest of Featherbed Bank - Black Ledge

22 0.10 0.01 12.32 North of Featherbed Bank - Black Ledge

23 0.61 0.02 72.25 Intracoastal Waterway

24 MD 0.16 MD Shoal Area

25 MD 0.09 MD Rickenbacker Causeway

64 0.66 ND 78.20 Dinner Key

66 0.90 0.13 106.06 Coral Gables Canal

68 0.20 0.52 23.08 Coral Gables Canal

84 0.92 0.20 107.90 Featherbed Bank

87 1.50 0.07 176.24 Southeast of Black Point

96 0.72 0.15 84.02 Caesar Creek

101 MD 0.12 215.32 Goulds Canal and Black Creek

102 0.88 0.22 108.61 C-102 Canal

103 6.67 0.10 783.49 Military Canal

105 0.45 ND 53.25 Mowry Canal

120 MD ND 29.57 Key Largo

122 MD ND MD Intracoastal Waterway

125 MD 0.22 51.89 South of Turkey Point

128 0.30 0.34 35.03 Turkey Point Power Plant Barge Canal

.c8.Table 16. Aliphatic hydrocarbon characterization of tissue samples
collected during Year 01. All values are corrected for percent recovery
and expressed on a dry weight bases.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory/ f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

Sample (µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

Sea Trout #1 (*Cynoscion arenarius*)

ND ND ND ND ND ND ND ND ND ND ND ND

Sea Trout #2 (*Cynoscion arenarius*)

10.68 1.6 ND ND ND ND ND ND ND ND ND ND

Pinfish (*Lagodon rhomboides*)

3.66 23.0 ND ND ND ND 0.73 ND ND ND C12-C15 0.64

Grey Snapper (*Lutjanus griseus*)

36.49 11.8 ND ND ND ND 1.22 ND ND ND ND ND

Scallops (*Argopecten* spp.)

589.83 53.7 ND ND ND ND 0.71 ND 2.82 ND ND ND

Toadfish (*Opsanus beta*)

22.40 6.7 ND ND ND ND 1.07 ND ND ND ND ND

Shrimp (*Penaeus* spp.)

12.05 1.4 ND ND ND ND 1.13 ND ND ND C12-C15 1.19

Grunt (*Haemulon* sp.)

16.04 2.5 ND ND ND ND 0.76 ND ND ND C12-C16 1.83

Stone Crab (*Menippe mercenaria*)

> Hepatopancreas

ND ND ND ND ND ND ND ND ND ND ND ND

> Claw muscle

19.90 0.6 ND ND ND ND ND ND ND ND ND ND

Blue Crab (*Callinectes sapidus*)

> Hepatopancreas

0.21 ND ND ND ND ND ND ND ND ND ND ND

> Claw muscle

ND ND ND ND ND ND ND ND ND ND ND ND

School Master (*Lutjanus apodus*)

1.68 0.1 ND ND ND ND ND ND ND ND ND ND

.c8.Table 17. Aromatic hydrocarbon characterization of tissue samples
collected during Year 01. All values are corrected for percent recovery
and expressed on a dry weight basis.

Total

Sample f2 Napththalene Phenanthrene Dibenzothiophene Pyrene

Sea Trout #t 36.77 ND ND ND ND

(*Cynoscion arenarius*)

Sea Trout #2 6.48 ND ND ND ND

(*Cynoscion arenarius*)

Pinfish 0.16 ND ND ND ND

(*Lagodon rhomboides)*

Grey Snapper 3.08 0.63 ND ND ND

(*Lutjanus griseus*)

Scallops 10.99 ND ND ND ND

(*Argopecten* spp.)

Toadfsh 3.39 ND ND ND ND

(*Opsanus beta*)

Shrimp 85.66 ND ND ND ND

(*Penaeus* spp.)

Grunt 6.32 2.63 1.49 ND 2.27

(*Haemulon* sp.)

Stone Crab

(*Menippe mercenaria*)

> Hepatopancreas 5.55 ND ND ND ND
>
> Claw muscle 32.47 ND ND ND ND

Blue Crab (*Callinectes sapidus*)

> Hepatopancreas 91.47 ND 0.05 0.62 5.75
>
> Claw muscle 29.27 5.81 ND ND 2.90

School Master 65.09 ND ND 6.78 14.32

(*Lutjanus apodus*)

> traffic and is a major area for on and off loading cargo, ship
> building, repair and refurbishing. The River was dredged in and
> widened 1933 (Austin, 1971) thus the accumulation of hydrocarbons in
> the sediment has been during a 50-year time span. This area was chosen
> because of its use as a port facility and intensive industrialization.
> In addition with the growing economy of Miami this area will receive
> greater pressure from ship traffic in the future.
>
> The areas located in the southern area of the Bay are Snapper Creek,
> Black Creek - Goulds Canal, and Military Canal. Black Creek and Goulds
> Canal are both water-control canals which intersect before emptying
> into the Bay. The sample collected during the first year study was at
> this intersection and indicated petroleum contamination. The landward
> portion of Goulds Canal runs parallel to an abandoned landfill, and
> the Black Creek area is under development by Dade County. A proposed
> public park and marina are to be built there. Military Canal also
> showed elevated concentrations of hydrocarbons with indices
> characteristic of petroleum. This canal is also a water-control
> structure and receives no boat traffic. The canal drains from the
> Homestead Air Force Base and the surrounding communities. Snapper
> Creek was chosen because of its location in a predominantly
> residential area.
>
> Nine areas were sampled for surface water in the Bay. Six of these
> areas were canals, one was the Port of Miami, and the other two were
> in open water located in northern and southern areas of the Bay. Five
> of these areas contained petroleum contamination in their surface
> waters. The areas were as follows: the Miami River, Little River,
> Goulds Canal, Military Canal, and Government Cut (Port of Miami).
> Tables 18 and 19 present the results of the hydrocarbon analysis of
> the surface waters. A detailed description of the analyses are
> presented in Appendices F and G.
>
> The Miami River was sampled for surface waters during an ebbing tide.
> Samples were collected while progressively moving inland. This insured
> that different water masses were sampled. Samples 205, 206 and 221
> were all taken in the mouth of the Miami River and show no indications
> of petroleum contamination. Sample 211 which was collected in the
> upper most reaches of the river (the railroad bridge) accessible by
> the collection vessel also showed no indication of contamination.
> Samples 207 to 210 and 212 all indicate petroleum contamination.
> Figure 17 shows the chromatograms of the aliphatic fraction for
> surface water samples 207 and 208.
>
> The samples collected from the Little River showed basically the same
> pattern as those sampled from the Miami River. The samples collected
> in the north and south forks of the River (224 and 222, respectively)
> just before it enters the Bay show no indication of petroleum
> hydrocarbons. Although samples 226 and 227 collected landward
> contained petroleum hydrocarbons.
>
> Samples collected from Goulds Canal and Military Canal showed the same
> trend as the other canals sampled. The concentration of petroleum in
> the surface waters increase as one moves inland. Figure 18 shows the
> chromatograms for the aliphatic fraction of the three samples
> collected in Goulds Canal, 232, 233, and 234. Figure 19 shows the
> chromatogram of the aliphatic fraction for sample 238 which was
> collected from Military Canal.
>
> Table 20 and 21 presents the hydrocarbon characterization for the
> sediment samples. Six areas were sampled (Miami River, Little River,
> Goulds Canal, Black Creek, Military Canal, and Snapper Creek), and all
> contained petroleum contaminants except the Snapper Creek sample. The
> Miami River contained the highest concentrations of total hydrocarbons
> 1833.46 µg/g.
>
> .c8.Table 18. Aliphatic hydrocarbon characterization of water samples
> collected during Year 02. All values are corrected for percent
> recovery.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory/ f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

Sample (µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

> Miami River

205 0.66 0.14 ND ND ND 0.08 0.01 ND ND ND C14-C28 0.37

206 0.46 0.04 ND ND ND ND ND ND ND ND C18-C25 1.86

207 5.27 11.46 0.27 1.05 1.96 1.60 0.03 0.12 0.06 ND C14-C27 1.27

208 14.07 54.11 0.94 0.48 2.27 2.10 ND 0.04 0.09 0.31 C17-C30 0.23

209 3.46 17.30 0.30 1.23 ND 0.96 ND ND 0.03 ND C16-C26 3.28

210 4.42 0.07 0.23 0.37 22.10 1.01 0.01 0.17 0.05 ND C15-C26 3.28

211 2.13 0.11 ND 0.75 ND 0.58 ND ND 0.01 ND C18-C26 22.88

212 3.33 0.06 0.22 2.25 2.31 2.12 ND 0.05 0.02 ND C16-C25 5.82

221 1.92 0.30 ND ND 0.62 ND ND 0.03 0.03 ND C17-C30 0.63

Little River

222 2.79 0.32 ND ND ND ND ND ND 0.04 ND C21-C30 1.14

224 0.27 0.14 ND 1.70 2.65 ND 0.01 0.03 TD ND C15-C25 1.75

226 0.98 0.44 0.42 3.33 0.42 1.36 0.01 0.01 TD ND C15-C30 0.45

227 8.82 4.12 0.08 0.39 5.14 0.98 ND 0.04 0.04 ND C16-C28 0.94

Goulds Canal

232 25.36 9.57 0.38 1.03 1.16 1.44 0.16 0.36 0.21 ND C14-C30 0.54

233 4.24 5.89 ND 1.31 1.46 1.71 0.04 0.21 0.09 ND C15-C28 1.07

234 2.69 44.83 ND ND ND ND 0.17 ND ND 0.26 C16-C29 0.43

Black Creek

241 2.00 16.67 ND ND ND ND 0.07 0.04 0.03 ND C14-C28 0.49

242 1.07 9.73 ND ND ND ND ND ND ND ND ND ND

246 0.41 1.11 ND ND ND ND ND ND 0.02 ND C12-C27 4.65

Military Canal

238 6.17 10.28 0.11 ND ND ND ND 0.03 0.01 ND C17-C27 1.58

240 2.16 8.31 ND ND ND ND ND ND ND ND C16-C28 0.62

Snapper Creek

247 0.81 5.4 ND ND ND ND ND ND ND ND C22-C28 0.15

Government Cut

231 3.13 3.44 1.46 2.56 0.25 1.02 ND 0.01 0.01 ND C16-C28 1.95

> Table 18. Aliphatic hydrocarbon characterization of water samples
> collected during Year 02. All values are corrected for percent
> recovery (cont.).

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory/ f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

Sample (µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

Open Water-Northern Bay

230 0.40 0.29 ND ND 0.89 ND 0.08 0.02 ND ND C15-C25 32.97

Open Water-Southern Bay

235 3.95 16.46 ND ND ND ND ND ND 0.06 Nd C19-C26 1.39

236 10.18 42.42 ND ND ND ND ND ND ND ND ND 0.26

237 0.95 1.30 ND ND ND 1.26 ND 0.01 0.04 ND C17-C28 1.11

> ND = None Detected
>
> TD = Trace Detected
>
> .c8.Table 19. Aromatic hydrocarbon characterization for water samples
> collected during Year 02. All values are corrected for percent.

Total Dibenzo= Phenanthrene 1-Methyl=

Sample f2 Napththalene thiophene (µg/L) phenanthrene Pyrene

> Miami River

205 4.57 ND ND ND ND ND

206 10.61 ND ND ND ND ND

207 0.46 ND ND ND ND 0.01

208 0.26 ND ND ND ND ND

209 0.20 ND 0.01 ND ND 0.01

210 60.05 ND 0.05 0.03 0.14 0.42

211 19.59 ND 0.02 ND ND ND

212 50.75 ND 0.61 ND ND ND

221 6.48 ND ND ND ND 0.03

Little River

222 8.68 ND ND ND ND 0.03

224 1.97 ND ND ND ND ND

226 2.21 ND ND ND ND 0.01

227 2.14 ND 0.08 0.04 ND ND

Goulds Canal

232 2.65 ND 0.01 0.01 0.02 ND

233 0.72 ND ND N 0 ND 0.69

234 0.06 ND ND ND ND ND

Black Creek

241 0.12 ND 0.01 ND ND ND

242 0.11 ND ND ND ND ND

246 0.37 ND 0.04 0.03 ND ND

Military Canal

238 0.60 ND ND ND ND ND

240 0.26 ND ND ND ND ND

Snapper Creek

247 0.15 ND ND ND ND ND

Government Cut

231 0.91 ND ND ND ND ND

> Table 19. Aromatic hydrocarbon characterization for water samples
> collected during Year 02. All values are corrected for percent
> (cont.).

Total Dibenzo= Phenanthrene 1-Methyl=

Sample f2 Napththalene thiophene (µg/L) phenanthrene Pyrene

Open water-Northern Bay

230 1.39 ND ND ND ND ND

Open Water-Southern Bay

235 0.24 ND ND ND ND ND

236 0.24 ND ND ND ND ND

237 0.73 ND ND ND ND ND

> ND = None detected.

![](media/image24.pct){width="5.972222222222222in"
height="6.680555555555555in"}

.c7.Figure 17. Chromatograms of aliphatic (f1) fraction. Surface water
samples collected in the Miami River. a) sample #207, b) sample #208.

![](media/image25.pct){width="5.388888888888889in"
height="8.152777777777779in"}

> .c7.Figure 18. Chromatograms of aliphatic (f1) fraction. Surface water
> samples collected in Goulds Canal.
>
> ![](media/image26.pct){width="5.944444444444445in"
> height="4.041666666666667in"}
>
> .c7.Figure 19. Chromatograms of aliphatic (f1) fraction. Surface water
> sample #238 collected in Military Canal.
>
> .c8.Table 20. Aliphatic hydrocarbon characterization of sediment
> samples collected during Year 02. All values are corrected for
> recovery and expressed on a dry weight basis.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

(µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

> Miami River

213

(0-5) 26.40 2.3 ND 0.38 2.38 1.54 ND 0.40 ND ND C16-C28 0.06

214

(0.-5) 531.13 13.5 0.16 2.74 0.27 0.59 1.01 1.46 0.69 3.91 C12-C29 2.22

(20-25) 322.50 15.4 0.16 2.70 0.10 0.91 0.39 0.21 ND ND C14-C19 0.65

215

(0-5) 456.98 14.5 0.12 0.15 0.79 1.16 0.13 0.20 2.25 ND C15-C21 0.77

216

(0-5) 1662.40 9.7 0.21 1.11 0.29 0.25 3.46 4.62 ND ND C14-C20 1.94

217

(0-5) 342.68 24.7 0.14 0.24 0.37 0.66 0.15 0.13 ND ND C14-C20 0.83

218

(0-5) 55.99 12.4 0.11 0..67 1.06 0.61 0.10 0.21 ND ND C15-C19 0.97

(20-25) 169.52 20.6 0.17 0.22 0.49 0.64 0.09 0.03 ND ND C15-C28 0.15

(60-65) 1462.15 26.8 0.43 1.97 0.18 1.24 1.10 2.35 ND ND C12-C20 0.64

219

(0-5) 534.37 9.3 0.13 4.93 0 0.87 0.43 ND ND ND C14-C18 0.31

220

(0-5) 206.15 11.1 0.16 1.99 0.06 0.57 0.27 0.11 0.61 ND C14-C25 2.09

> Little River

223

(0-5) 0.90 14.6 ND ND ND ND ND ND ND ND ND ND

225

(0-5) 13.99 3.6 1.25 5.78 0.05 1.85 0.02 0.01 0.44 0.36 C12-C30 1.67

(25-30) 7.12 24.6 ND ND ND ND ND ND ND ND ND ND

(55-60) 4.07 1.0 ND ND ND ND ND ND ND ND ND ND

228

(0-5) 2.65 1.2 ND ND 0.40 ND ND 0.06 ND 1.34 ND ND

229

(0-5) 39.09 4.6 0.06 ND ND ND ND 0.42 ND ND ND 1.37

> Goulds Canal

232

(0-5) 227.68 15.8 0.13 0.84 0.25 0.12 0.11 0.42 ND ND C15-C19 4.00

(55-60) 413.08 9.9 0.16 7.84 0.09 0.15 0.29 0.41 ND ND C15-C20 3.36

233

(0-5) 165.99 2.0 0.03 1.33 ND ND ND ND ND ND ND ND

234

(0-5) 14.69 1.11 ND 5.28 0.12 0.41 ND 0.12 0.47 ND C17-C27 20.43

> Table 20. Aliphatic hydrocarbon characterization of sediment samples
> collected during Year 02. All values are corrected for recovery and
> expressed on a dry weight basis (cont.).

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

(µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

> Black Creek

241

(0-5) 16.25 1.7 0.68 7.41 ND 0.44 0.03 ND 0.44 ND C12-C28 0.55

242

(0-5) 3.03 1.1 ND ND ND ND ND 0.59 ND ND ND ND

243

(0-5) 1.99 0.3 ND ND ND ND 0.86 ND ND ND ND ND

244

(0-5) 37.18 0.6 ND 11.45 ND ND ND ND 1.95 ND C16-C21 0.76

245

(0-5) 23.57 7.6 0.99 14.18 ND 0.38 ND ND 1.06 4.65 C18-C29 10.42

246

(0-5) 0.35 0.2 ND ND ND ND N 0 ND ND ND ND ND

> Military Canal

239

(3-5) 29.50 3.7 1.20 2.41 0.26 ND ND 0.07 0.91 ND C17-C24 0.09

239

(0-5) 4.84 0.8 ND ND ND ND ND 0.16 ND ND C17-C19 3.7S

240

(0-5) 269.31 8.0 0.24 14.12 0.11 3.23 0.22 0.32 1.88 ND ND ND

(60-65) 3.45 0.6 ND ND ND ND ND ND ND ND ND ND

(120-125) 6.29 5.2 ND ND ND ND ND ND ND ND ND ND

Snapper Creek

247

(0-5) 0.22 0.1 ND ND ND ND ND ND ND ND ND ND

> ND = None Detected
>
> .c8.Table 21. Aromatic hydrocarbon characterization of sediment
> samples collected during Year 02. All values corrected for percent
> recovery.

Total Dibenzo= Phenanthrene 1-Methyl=

Sample f2 Napththalene thiophene (µg/L) phenanthrene Pyrene

> Miami River

213 (0-5) 11.38 ND 0.11 2.84 0.84 4.03

214 (0-5) 39.39 ND 0.12 1.22 0.26 3.10

(20-25) 20.96 ND 0.31 0.13 0.11 9.55

215 (0-5) 31.53 ND 0.34 ND 0.24 ND

216 (0-5) 171.06 1.74 3.69 0.90 0.50 2.46

217 (0-5) 13.86 ND 0.07 0.29 0.29 0.14

218 (0-5) 4.52 ND 0.06 0.41 0.05 0.60

(20-25) 8.21 ND 0.15 0.62 0.10 1.25

(60-65) 54.62 ND 1.05 1.16 0.51 1.65

219 (0-5) 57.30 0.18 0.55 0.28 0.60 2.06

220 (0-5) 18.62 ND 0.16 1.16 0.13 1.50

Little River

223 (0-5) 16.20 ND 0.08 0.87 0.17 2. 50

225 (0-5) 3.91 ND 0.03 0.15 0.07 0.48

(25-30) 0.29 ND 0.12 ND ND ND

(55-60) 4.24 ND 0.18 ND 0.05 ND

228 (0-5) 2.13 ND 0.05 0.08 ND 0.35

229 (0-5) 8.44 ND 0.48 0.17 0.36 ND

Goulds Canal

232 (0-5) 14.40 ND 0.50 TD 0.09 0.08

(55-60) 41.97 ND 0.32 0.06 0.32 0.91

233 (0-5) 84.98 ND 4.05 ND 1.19 1.72

234 (0-5) 13.23 ND 0.42 ND 0.62 ND

Black Creek

241 (0-5) 9.55 0.04 0.05 0.18 0.36 0.32

242 (0-5) 2.90 ND 0.05 0.13 0.10 0.18

243 (0-5) 6.74 ND ND 0.11 0.33 0.52

244 (0-5) 66.79 ND 0.14 1.64 2.91 2.89

245 (0-5) 3.73 ND 0.15 ND 0.10 0.02

246 (0-5) 4.54 ND ND 0.08 0.23 ND

Military Canal

238 (0-5) 7.74 ND 0.14 ND 0.16 ND

239 (0-5) 6.42 ND ND 0.09 0.02 0.34

240 (0-5) 22.86 ND 0.21 1.15 0.02 0.82

(60-65) 5.51 ND ND ND ND ND

(120-125) 1.22 ND 0.03 0.04 ND 0.10

Snapper Creek

247 (0-5) 1.51 ND 0.07 ND 0.09 ND

TD - None Detected.

> TM - Trace Detected.
>
> All of the sediments collected from the Miami River contained
> petroleum hydrocarbons except sample 213 which was collected in the
> Tamiami Canal at the 37 Avenue bridge. The River had the highest
> concentrations of hydrocarbons by a factor of 10 than any other
> sampling sites. One of the very interesting results of the down core
> analysis for samples 214 and 218 was that petroleum contaminant was
> detected as deep as 65 cm (Figure 20 and 21). Another interesting
> occurrence was that the concentration of hydrocarbons increased with
> depth for sample 218 at the three depths sampled. The possible cause
> for the rather complete mixing of the sediments in\
> the three depths sampled. The possible cause for the rather complete
> mixing of the sediments in the Miami River is undoubtedly due to the
> heavy ship traffic re suspending the bottom sediments. Especially that
> of the river tugs with their large, full pitch propellers. This
> phenomena was observed during the sampling operations.
>
> Two samples, 225 and 229, from the Little River contained petroleum
> contamination. Both samples were located in the north fork of the
> river. Down core analyses on sample 225 showed no contamination below
> the surface layer (Figure 22).
>
> Goulds Canal showed petroleum contamination in two of the three
> sediment samples collected. The contamination at depth and the
> increase in concentration with depth is also present in sample 232.
> The chromatograms for the aliphatic fraction, for both depths are
> presented in Figure 23. The same explanation for mixing applied to the
> Miami River cannot be used to explain the high concentrations of
> hydrocarbons at the greater depths in Goulds Canal. Sample 232 was
> obtained at the end of the Canal next to an earthen dike. A possible
> explanation for this is that the stagnation of the water caused by the
> dike had created a sink or that down canal sediment had been used as
> fill.
>
> Only two samples collected from Black Creek showed any petroleum
> contamination. Sample 241 was located inland from the intersection of
> Black Creek and Goulds Canal and sample 245 was located in a large
> open basin used for boat launchings.
>
> Two of the three samples collected from Military Canal contained
> petroleum contamination. Sample 240 which was subjected to down core
> analysis exhibited contamination only in the surface layer (Figure
> 24).
>
> Biota analyses consisted of fish, shrimp, crabs, rays, bivalves and
> oysters. Tables 22 and 23 presents the aliphatic and aromatic data,
> respectively. The bivalves and oysters were collected from Black
> Creek, the flat tree oysters were collected from a marina located on
> Virginia Key, the other samples were collected from open areas of the
> Bay. The flat tree oyster was the only organism containing petroleum
> contamination. Figure 25 is the chromatogram of the aliphatic fraction
> for this sample.
>
> ![](media/image27.pct){width="5.916666666666667in"
> height="6.819444444444445in"}
>
> .c7.Figure 20. Chromatograms of aliphatic (f1) fraction. Miami River
> sediment sample #214.
>
> ![](media/image28.pct){width="5.041666666666667in"
> height="8.63888888888889in"}
>
> .c7.Figure 21. Chromatograms of aliphatic (f1) fraction. Miami River
> sediment sample #218.
>
> ![](media/image29.pct){width="5.152777777777778in"
> height="8.26388888888889in"}
>
> .c7.Figure 22. Chromatograms of aliphatic (f1) fraction. Little River
> sediment sample #225.
>
> ![](media/image30.pct){width="5.888888888888889in"
> height="6.555555555555555in"}
>
> .c7.Figure 23. Chromatograms of aliphatic (f1) fraction. Goulds Canal
> sediment sample #232.
>
> ![](media/image31.pct){width="5.180555555555555in"
> height="8.041666666666666in"}
>
> .c7.Figure 24. Chromatograms of aliphatic (f1) fraction. Military
> Canal sediment sample #240. a) 0-5 cm depth, b) 60-65 cm depth, c)
> 120-125 cm.
>
> .c8.Table 22. Aliphatic hydrocarbon characterization of tissue samples
> collected during Year 02. All values are corrected for percent
> recovery and expressed on a dry weight bases.

KEY n-

Total\* RATIOS HYDROCARBONS ALKANES

Laboratory/ f1 f1/ Resol. Prist./ C17/ C18/ (µg/g) Homol.

Sample (µg/g) f2 Unres Phyt. Prist. Phyt. 1500 1700 2085 2900 Ser. CPI

Butterfly Ray (*Gymnura micrura*)

159.33 43.7 ND ND ND ND 0.05 ND 0.19 ND C15-C28 0.01

Catfish (*Arius felis*)

108.44 13.5 7.74 ND ND ND 0.10 ND 5.37 ND C15-C28 0.22

Grunt (*Haemulon scrurus*)

70.64 29.9 ND ND ND ND ND ND ND ND C24-C28 0.29

Pigfish (*Orthopristis* *chrysopterus*)

62.93 2.4 ND ND ND ND ND ND ND ND ND ND

Shrimp (*Penaeus* sp.)

0.33 ND ND ND ND ND ND ND ND ND ND ND

Crab (*Callinectes* *ornatus*)

ND ND ND ND ND ND ND ND ND ND ND ND

Blue Crab (*Callinectes sapiches*)

24.45 0.1 ND ND ND ND ND 0.76 ND ND C20-C23 0.21

Mixed bivalves (*Mytilopsis leucophacata* and *Brachidontes exustus*)

16.61 ND ND ND ND ND ND ND ND ND ND ND

Oyster (*Crassostrea* *virginica*)

ND ND ND ND ND ND ND ND ND ND ND ND

Flat Tree Oyster (*Isognomon alatus*)

125.20 2.8 0.41 0.60 0.04 0.11 ND 0.08 2.65 8.92 C17-C30 0.22

ND = None Detected

> .c8.Table 23. Aromatic hydrocarbon characterization of tissue samples
> collected during Year 02. All values are corrected for percent
> recovery and expressed on a dry weight bases.

Total f2 Naphthalene Dibenzo- Phenan- 1-Methyl- Pyrene

Sample (µg/g) thiophene threne phenanthrene

Butterfly Ray 3.65 ND ND ND 0.03 ND

(*Gymnura micrura*)

Catfish 8.02 0.54 0.15 0.11 0.40 ND

(*Arius felis*)

Grunt 2.36 ND ND ND ND ND

(*Haemulon scrurus*)

Pigfish 26.52 ND ND ND 1.19 ND

(*Orthopristis* *chrysopterus*)

Shrimp ND ND ND ND ND ND

(*Penaeus* sp.)

Crab 53.99 ND ND ND 4.89 11.05

(*Callinectes* *ornatus*)

Blue Crab 192.09 ND ND ND 4.05 30.58

(*Callinectes sapiches*)

Mixed bivalves ND ND ND ND ND ND

(*Mytilopsis leucophacata* and *Brachidontes exustus*)

Oyster 138.16 ND ND ND ND 132.66

(*Crassostrea* *virginica*)

Flat Tree Oyster 57.51 ND ND ND 6.00 14.50

(*Isognomon alatus*)

ND - None Detected

> ![](media/image32.pct){width="5.958333333333333in"
> height="3.5555555555555554in"}
>
> .c7.Figure 25. Chromatograms of aliphatic (f1) fraction. Flat tree
> oyster collected from marina.
>
> .c2.4.5. Summary
>
> During the two year duration of this study 205 surface sediments, 21
> biota and 27 surface water samples were collected and analyzed for
> hydrocarbon content. The total hydrocarbon content in the surface
> sediments ranged from below our detection limits to 2663.4 µg/g. The
> surface waters ranged from 0.8 to 64.5 µg/L and the biota samples
> ranged from 0.3 to 600.8 µg/g. The samples containing the highest
> concentrations for both water and sediment were collected from the
> Miami River. The concentration of hydrocarbons found in the sediment
> of the Miami River are as high as those found in Chesapeake Bay, New
> York Bight (Table 24) and at least ten times greater than those in
> Charlotte Harbor and the St. Johns River.
>
> The sediments were the best indicator of petroleum contamination since
> they are the ultimate sink for this pollutant. The surface sediment
> samples which contained petroleum contaminants were usually associated
> with two main usage patterns: 1) areas associated with boats and ships
> (e.g., major transportation routes, moorings, cargo handling, and
> construction and maintenance); and 2) areas which receive runoff and
> other inputs from highly urbanized regions of Dade County.
>
> The information gathered during this two-year study has established a
> baseline for the spatial distribution of hydrocarbons in Biscayne Bay.
> This database will be most useful in future studies for establishing
> levels of contamination from oil spills or other sources of petroleum
> contaminants. It has also established a benchmark from which future
> changes in the concentration and distribution of hydrocarbons can be
> compared.
>
> .c8.Table 24. Summary of petroleum hydrocarbon concentrations in
> surface sediments for different geographical areas.
>
> Total
>
> Location Hydrocarbons Aliphatics Aromatics Citation
>
> µg/g µg/g µg/g
>
> COASTAL AREAS
>
> Australia
>
> Western Port Bay 42 - - Burns and Smith, 1977
>
> (polluted area)
>
> Western Port Bay 7 - - Burns and Smith, 1977
>
> (unpolluted area)
>
> Bermuda
>
> South Shore 262 42 221 Sleeter, 1980
>
> inside boiler reefs
>
> Chesapeake Bay 3200 1950 1210 Walker *et al.*, 1975
>
> Dungeness Bay - 3 30 Macleod *et al.*, 1977
>
> (Juan de Fuca)
>
> English Channel 31 - - Tissier and Oudin, 1973
>
> Narragansett Bay
>
> Providence River 2060 Farrington and Quinn, 1977
>
> West Passage 263 - - Farrington and Quinn, 1977
>
> Upper Bay 1990 1900 29 Zatrion, 1973
>
> New York Bight 1346-2900 866-1800 479-1100 Farrington and Tripp, 1977
>
> Orinoco Delta 59 30 28 Smith, 1954
>
> Port Angeles H. - 530 260 Macleod *et al.*, 1977
>
> (Juan de Fuca)
>
> CONTINENTAL SHELFS
>
> Bermuda 19 7 12 Sleeter, 1980
>
> Black Sea 170 - 34 Shishenina *et al.*, 1974
>
> California Shelf - 36 64 Smith, 1954
>
> Gulf of Mexico
>
> South Eastern area 5 3 2 Lytle and Lytle, 1977
>
> Eastern area 2 2 2 Lytle and Lytle, 1977
>
> North Central area 4 2 2 Gearing *et al.*, 1976
>
> Table 24. Summary of petroleum hydrocarbon concentrations in surface
> sidements for different geographical areas (cont.).
>
> Total
>
> Location Hydrocarbons Aliphatics Aromatics Citation
>
> µg/g µg/g µg/g
>
> North Atlantic
>
> Hudson Canyon 16 5 11 Farrington and Tripp, 1977
>
> Hudson Channel 81 35 60 Farrington and Tripp, 1977
>
> Continental shelf 11 5 5 Farrington and Tripp, 1977
>
> Continental slope 14 5 9 Farrington and Tripp, 1977
>
> Norwegian Sea 11 - 3 Shishenina *et al.*, 1974
>
> Scotian Shelf
>
> Halifax transect 2 - - Keizer *et al.*, 1977
>
> Well sites 1 - - Keizer *et al.*, 1977
>
> Sable Island 3 - - Keizer *et al.*, 1977
>
> West Africa
>
> West of Cape Verde 33 20 12 Smith, 1954
>
> Southwest of 29 17 13 Smith, 1954
>
> Cape Verde
>
> ABYSSAL PLAIN and OPEN OCEAN
>
> Pacific 14-16 - 3 Shishenina *et al.*, 1974
>
> Norwegian Sea 10 - 3 Shishenina *et al.*, 1974
>
> North Atlantic 5 3 2 Farrington and Tripp, 1977
>
> Canary Islands 12 2 10 Sleeter, 1980
>
> .c1.5. Acknowledgments
>
> The authors would like to acknowledge the following people at the
> Rosenstiel School of Marine and Atmospheric Science for their
> scientific, technical and monetary support: Associate Dean Warren
> Wisby and Dr. Richard Robins for supplying the funds to refurbish the
> analytical laboratory, Dr. Harold Wanless for his valuable input
> concerning the geology of Biscayne Bay, Mr. Steve Berkeley and Mr.
> Steve Carney for their assistance in acquisition of the biota samples,
> Todd S. Payne, Ludy Diaz de Carrasco, Emilio Perez and Richard
> Fitzpatrick who were of great assistance in maintaining the everyday
> operation of the laboratory; Mark Pikur, Enrique Lahmann and Christy
> Thomas for their assistance with the field collections, Mrs. Kay Hale
> and her excellent library staff for their valuable assistance, Shelley
> McCarthy for her kindness, patience and excellent job typing the
> manuscript and Catherine Sikkema who prepared the graphics. We would
> like to thank the Dade County Department of Environmental Resources
> Management for letting us participate in the Biscayne Bay Restoration
> and Enhancement Program and all the members of this group for their
> valuable input and cooperation. We
>
> certainly appreciate the constructive input and assistance supplied by
> the project reviewer Dr. Pat Parker. The assistance and cooperation
> supplied by the Mote Marine Laboratory and Jacksonville University is
> also appreciated. Our thanks are expressed to Dr. Edward S. Van Vleet
> for his excellent GC-MS work and to Alan Huff, the Project Officer,
> for his kindness, patience, and administrative assistance.

\[Rescue of this work in 2005 was funded through a grant of the South
Florida Ecosystem Restoration Prediction and Modeling Program (SFERPM) -
a competitive program conducted by the Center for Sponsored Coastal
Ocean Research (CSCOR), in association with the South Florida Living
Marine Resources Program (SFLMR) - for Coastal and Estuarine
Data/Document Archeology and Rescue (CEDAR) for South Florida. We wish
to thank J. Browder, S. Markley, R. Skinner, A. Gangitano, G. G.
Lauenstein and M. J. Bello for their assistance.\]

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