E PA- 600/2-

76-160a June 1976

IERL-RTP PROCEDURES MANUAL: LEVEL 1 ENVIRONMENTAL ASSESSMENT

by •-.W. Hamersma,

S.L, Reynolds,

and R.F. Maddalone TRW Sys[ems

Group One Space Park Redondo B•ach,

California

90278

Contract No. 68-02-1412,

Task 18 ROAP No. 21AAZ-015 Program Element

No. lAB013

EPA Project

Officer:

Robert

M. Statnick Industrial Environmental

Research

Laboratory Office of Energy,

Minerats,

and Industry Research Trlangle

Park, NC 27'/II Prepared for U.S. ENVIRONMENTAL PROTECTION

AGENCY Office of Research

and Development Washington, DC 20460PREFACE
The Process

Measurements

Branch,

IERL/RTP,

has developed

andrecommended the implementation

of a phased

sampling

and analytical

strategy

for Environmental Assessment

Programs.

The first phase,

Level l, has as its goal the quantification

of mass emissions

within

a factor

of 2 to 3 for inorganic elements

and organic

classes.

The second

phase,

Level 2, has as its goal the quantification

and identification

of specific

compounds. The third phase,

Level 3, has as its goal the continuous

monitoring

of indicator compounds

as surrogates

for a large number

of specific

compounds. This document

represents

the first time that a set of integrated sampling and analytical

procedures

for environmental

assessment

programs has been compiled.

As such, it is anticipated

that many readers

might take exception

with specific

sampling

and/or

analytical

tools;

however,

we feel that the recommended

environmental

assessment

system

is both valid and information

effective. IERL/RTP Contractors

or Grantees

will use the system

described

in this document

for Environmental

Assessment

Programs.

It is anticipated that non-IERL/RTP

organizations

who are active

in the environmental assessment field will also utilize

this manual. This manual

has been made as specific

as possible,

although

it is recognized that it is impossible

to specify

the exact sampling

and analysis procedure

for every possible

circumstance.

When situations arise where alternative

Level l sampling

and analysis

procedures

are necessary or desired,

the contractor

is directed

to submit

his alternate plan to his project

officer

and the

Process

Measurements

Branch,

IERL-RTP, Research Triangle

Park, for approval

before

actual

work is initiated. I• •h•S docu•nt

becomes

universally

implemented,

then sets of comparable data will be generated

and prioritization

of the environmental insults associated

with differing

processes

can be made.

James A. Dorsey Chief, Process

Measurements

Branch iiiTRW Document

No. 24916-6040-RU-00 ABSTRACT

This manual

gives Level l procedures

(recommended

by Industrial Environmental Research

Laboratory--Research Triangle

Park) for personnel experienced in collecting

and analyzing

samples

from industrial

and energy producing

processes.

The phased

environmental

assessment

strategy provides a framework

for determining

industry,

process,

and stream priorities on the basis of a staged

sampling

and analysis

technique. Level l is a screening

phase that characterizes

the pollutant

potential of process

influent

and effluent

streams. The manual

is divided

into two major sections:

sampling

.procedures and analytical

procedures.

The sampling

section

is divided

into five chapters: fugitive

emissions,

gases,

aerosols,

liquids

(including

s•urries), and solids.

The analytical

section

is divided

into three chapters: inorganic, Organic,

and bioassays.ACKNOWLEDGEMENT

This work was conducted

under the direction

of Dr. R. !i. Statnick, EPA Task order •anage•and

administrative

direction

of Dr. L. D. Johnson, Industrial Environmental

Research

Laboratory,

Research

Triangle

Park, North Carolina.

The Applied

Chemistry

Department

of the Chemistry

and Materials Laboratory,

Applied

Technology

Division,

TRW Systems

and Energy, Redondo Beach,

California

was responsible

for the work performed

on this program. Dr. E. A. Burns,

Manager,

Applied

Chemistry

Department,

was Program Manager

and the

Task Order Manager

was Dr. J. W. Hamersma. Special acknowledgement

is given to the many helpful

discussions

with Mr. J. A. Dorsey,

and Drs. R. M. Statnick,

L. D• Johnson,

and C. H.Lochm•ller of the EPA during

the course

of this task order.

The extensive editorial and technical

assistance

provided

by S. C. Qui•livan

is also appreciated.The many helpful

comments,

suggestions,

and criticisms

from thefollowing PMB/IERL-RTP

Term Level of Effort

contractors

is also appreciated: Arthur D. Little,

Inc., Sampling

and Analysis

of Organic

l•aterials, Dr. P. L. Levins,

project

manager;

Research

Triangle

Institute,

Development of Environmental

Assessment

Control

Technology

Quality

Assurance Programs, Dr. F. Smith,

project

manager;

Aerotherm/Acurex CorD.,

Measurement Techniques

for High Temperature/High Pressure

Processes,

Inc., Mr. F. E. Moreno,

project

manager;

Southern

Research

Institute,

Particulate Sampling Support,

Dr. W. B. Smith,

Droject

manager;

and TRC, !•c., the Research Corporation

of New England,

Fugitive

Emissions

Methodology, Dr. H. J. Kolnsberg,

project

manager.

Special

recognition,

must be given to Dr. P. L. Levins,

Arthur

D. Little,

Inc. and Dr. H. J. Kolnsberg,

TRC, Inc., who provided

direct

input for Chapters

VIII and IV, respectively. The Process

Measurements

Branch

of IERL-RTP

is also acknowledged

for the input to Chapter

X.

vCONTENTS

INTRODUCTION CHAPTER I. STRATEGY

AND GENERAL

INFORMATION 1.1 D•finition

of Strategies 1.1.1 The Phased

Approach 1.1.2 Strategy

of the Phased

Approach 1.1.2.1 Definition

of Level I Sampling and Analysis 1.1.2.2 Definition

of Level 2 Sampling and Analysis 1.2 Multimedia

Sampling

Procedures 1.2.1 Classification

of Streams

for Sampling

Purposes 1.2.2 Phased

Approach

Sampling

Point Selection Criteria 1.2.3 Stream

Prioritization

Using the Phased

Approach 1.3 Data Requirements

and Pre-Test

Planning 1.3.1 Process

Data Needs 1.3.2 Pre-Test

site survey 1.3.3 Pre-Test

Site Preparation 1.4 Analysis

of Samples 1.5 Accuracy

and Precision

of Results CHAPTER II. GAS AND VAPOR SAMPLING

METHODOLOGY 2.1 Introduction 2.2 Sampling

Test Preparation 2.3 Gas Sampling

Techniques 2,3.1 High Pressure

Line Grab Samples 2.3.2 Slight

Positive

Pressure

Grab Purge Sampling 2.3.3 Negative

Pressure

Evacuated

Bulb Sampling 2.3.4 General

Considerations 2.4 Sampling

Procedures 2.4.1 Process

Streams,

Flues and Ducts 2.4.2 Vents 2.5 Sample

Handling xiiiii,I2

466
8111313141516172O2O20212222262627272828

viCONTENTS (Continued)

CHAPTER III. GASEOUS

STREAMS

CONTAINING

PARTICULATE

MATTER 3.1 Introduction 3.2 Particulate

Ma£ter

SamPling

Methodology 3..3 Preparing

for Sample

Collection 3.3.1 Pre.Site

Survey 3.3.2 Personnel

Requirements 3.3.3 Equipment

Preparation

for Sample

Collection 3.3.3.1 Precleaning

Procedures

for the SASS Train and Sample

Containers 3.3.3.2 Apparatus

Checkout 3.4 Series

Cyclone

Sampling

Procedure 3.5 Sample

Handling

and Shipment 3.6 Opacity

Measurements 3.7 Data Reduction CHAPTER IV. FUGITIVEEMISSIONS SAMPLING 4.1 Introduction 4.2 Airborne

Fugitive

Emissions 4.2.1 Preparation

for Sample

Collection 4.2.1.1 Pre-test

Site Survey 4.2.1.2 Measurement

Equipment 4.2.1.3 Personnel

Requirements 4.2.2 Sa•ling

Procedures 4.2.2.1 High Volume

sampler

Applications 4.2.2.2 SASS Train Sampler

Applications 4.2.2.3 Gas SamPles 4.2.3 Decision

Aid for Appropriate

Category

Selections 4.2.4 Sample

Handling

and Shipment 4.2.5 Data Reduction

for Airborne

Fugitive

Emissions 4.3 Waterborne

Fugitive

Emissions 4.3.1 Preparation

for Sample

Collection 4.3.1.1 Pre-test

Site Survey 4.3.1.2 Measurement

Techniques 4.3.1.3 Personnel

Requirements 29293435353536
3637384O414647474949495O54555557585859596060606061 viiCONTENTS (Continued)

4.3.24.3.34.3.44.3.5 Sampling

Procedures Decision Aid Sample Handling

and Shipment Data Reduction

for Waterborne

Fugitive

Emissions CHAPTER V. LIQUID

AND SLURRY

SAMPLING 5.1 Introduction 5.2 Preparing

for Sample

Collection 5.2.1 Pre-test

Site Survey 5.2.2 Personnel

Requirements 5.2.3 Equipment

Preparation 5.2.3.1 Sample

Containers 5.2.3.2 Apparatus 5.3 Sampling

Procedures 5.3.1 Heat Exchange

Sampling

Systems

for High Temperature Lines 5.3.2 Tap Sampling 5.3.3 Dipper

Sampling 5.4 Liquid

Sample

Handling

and Shipment CHAPTER VI. SOLID SAMPLING 6.1 Introduction 6.2 Pre-test

Site Survey 6.3 Solids

Sampling

Procedures 6.3.1 Shovel

Grab Sampling 6.3.2 Boring

Techniques 6.4 Sample

Collection

and Storage CHAPTER VII. LEVEL 1 INORGANIC

ANALYSIS

TECHNIQUES 7.1 Introduction 7.2. Level I Analysis

Methodology 7.2.1 Elemental

Analysis

by Spark Source

Mass Spectrometry 7.2.2 Wet Chemical

Analysis

for Hg, As, and Sb 7.2.3 Gas Chromatographic

Analysis

of Gaseous Components 7.2.4 Analysis

of Nitrogen

Oxides
viii 61616363656566666767676869697O7273767676777778798181848587
8991CONTENTS (Continued)

7.2.5 Analysis

of Leachable

Material 7.2.6 Analyses

Specific

for Aqueous

Samples CHAPTER VIII.

LEVEL 1 ORGANIC

ANALYSIS

TECHNIQUES 8.1 Introduction 8.2 Level I Organic

Analysis

Methodology 8.3 Sample

Preparation 8.3.1 Aqueous

Solutions 8.3.2 Solids,

Particulate

Matter

and Ash 8.3.3 Sorbent

Trap 8.4 Analysis

of Samples

for Organics 8.4.1 Gas Chromatographic

Analysis

of C I C 6 Range 8.4.2 Gas Chromatographic

Analysis

of C 7 C12 Range 8.4.3 Liquid

Chromatographic

Separation 8.4.4 Infrared

Analysis 8.4.5 Low Resolution

Mass Spectrometry CHAPTER IX. PARTICLE

MORPHOLOGY

AND IDENTIFICATION 9.1 Introduction 9.2 Particle

Characterization 9.2.1 Handling

Particles

for Microscopic

Examination 9.2.2 Photomicrography and Particle

Sizing

for Fugitive Emissions 9.2.3 Visual

Identification CHAPTER X. BIOLOGICAL

TESTING 10.1 Introduction 10.2 Health

Effects

Bioassays 10.2.1 Acute Toxicity

(In-vitro)

Test 10.2.2 Mutagenicity

(CarcinogenicitY) Screening

Test

10.3 10.2.3

LD50 Screening

Test Ecological Effects

Bioassays 10.3.1 Aquatic

Effects 10.3.2 Terrestri•al

Effects REFERENCES 9191939393969797979898I00101102102104104I05105
105107108108109109109110110110110112

ixCONTENTS (Continued)

APPENDIXESA Design

and Preparation

of a Field Testing

Unit A. 1 Advantages A.2 Components

and Layout B Process

Data Needs C Liquid

Chromatography

Separation

Procedure C.1 Procedure

for Column

Preparation C.2 Preparation

of the Sample C.3 Loading

Sample

on the Column C.4 Chromatographic

Separation

into 8 Fractions D Preparation

of XAD-2 Resin 118118119123127127127128129130

XILLUSTRATIONS

6.7.8.9.10.11.12.
13.14.15.
16.17.18.19.20.21.22.23.24.25.26.27.28.29.
31. Multimedia

Sampling

Approach

overview Basic Level Sampling

and Analytical

Scheme

for Particulates and Gases 9 Basic Level ISampling

and Analytical

Scheme

for Solids, Slurries,

Liquids i0 Typical Process

Flow Diagram

for Limestone

Venturi Spray Tower System 12 High Pressure

Line Grab Purge Sampling

Apparatus 23 Low Pressure

Grab Purge Sampling

Apparatus 24 Evacuated Grab Sampling

Apparatus 25 Source Assessment

Sampling

Schematic 30 Cyclones and Water Cooled

Probe 31 XAD-2 Sorbent

Trap Module 32 Flue Gas Sampling

Flow Diagram 33 Sample Handling

and Transfer

Nozzle,

Probe,

Cyclones and Filter 42 •ample Handling

and Transfer

XAD-2 Module 44 Sample Handling

and Transfer

Impingers 45 Sampling Categories

for Level 1 Airborne

Fugitive Emissions 48 Decision Example

for "Worst Case" Site 51 Expanded View of Connections

of XAD-2 Cartridge

to High Volume Sampler 53 Sampler Flow Rate Settings

for Dust 56 Plug Collector

for Fugitive

Water Samples 62 Level 1 Water Runoff

Fugitive

Emissions

Characterization 64 Sampling Methods

as a Function

of Stream

Type 65 SamRling Apparatus

for HPHT Lines 71 Field Handling

Scheme

for Liquid/Slurry

Samples 74 Multimedia Analysis

Overview 82 Level 1 Inorganic

Analysis

Flow Scheme 83 Sample Preparation

for SSMS Elemental

Analysis 86 Hg, Sb, As Sample

Preparation

and Analysis 88 Multimedia Organic

Analysis

Overview 94 Level 1 Organic

Analysis

Flow Diagram 95 Particle Characterization Flow Scheme 106 Level I Multimedia

Mobile

LabQratory 120 xiTABLES

Recommended Sample

Sizes and Detection

Limits SASS Train Impinger

System

Reagents List of Analyses

to be Performed

on Liquid/Slurry SamplesDecision Matrix

for Solid Sampling Recommended Gas Chromatographic

Parameters

for Analysis of Inorganic

and Organic Species Solvents Used in Liquid

Chromatographic

Separations Level i Mobile

Van Equipment Process •ata Needs for Phased

Environmental

Assessment Liquid Chromatography

Elution

Sequence Page1939
75789O

101
122124128

xiiINTRODUCTION This procedures

manual

has been prepared

for the Industrial

and Environmental Research

Laboratory

of the Environmental

Protection

Agency, Research Triangle

Park, North Carolina, It is written

so that the sampling

and analysis

professional

can plan and execute

the sampling

and analytical

portion

of a source

assessment

program. This manual

is not intended

for use by an inexperienced

professional staff or by technicians.

Analysis

procedures

are included

as schemes

with descriptions for all the samples

obtained

b.v the methods

delineated

in Chapters II through

VI. For those samples

which are analyzed

as part of the sampli.ng

procedure

and for those samples

which must be analyzed

on-site, reference is made to analysis

both in the sampling

and appropriate

analysis chapters.The sampling

procedures

in this manual

are designed

to be an integral part of the phased

environmental

assessment

and apply primarily

to Level I. The purpose

of this initial

effort

is to obtain

preliminary

environmental assessment information,

identify

problem

areas,

and provide

the basis for the prioritiz•tion

of streams,

components

and classes

of materials

for f•rther consideration

in the overall

assessment.

As such, the results

of the sampling

and of the corresponding

analysis

procedures

are quantitative within a factor

of + 2 to 3. A detailed

discussion

of the approach

along with the criteria

used for method

selection

is given in Chapter

I. In the preparation

of this manual

applicable

sampling

literature

was reviewed and a set of appropriate

sampling

procedures

for each of five sampling categories

was then defined.

Included

in these procedures

are criteria for sample

site selection,

sampling

equipment

and manpower

require- 'ments, amount

of sample

required,

and special

sample

preservation

techniques. Samples for which on-site

analyses

are necessary

are identified

along with the appropriate

procedures. Chapters II through

VI of this manual

center

around

five different types of Level l sampling

activities

that can be found in most industrial complexes: gas and vapor samples,

gaseous

streams

containing particulate matter, fugitive

emissions

sampling,

liquid

and slurry

sampling,

and solids

X'111sampling. In this way, the complex

and difficult

task of organizing

the manpower and equipment

necessary

for a successful

field test is facilitated. Each chapter

also includes

sections

on the general

problem,

preparations needed for the tests,

sampling

procedures,

and on-site

analysis

or packaging of samples

for shipment. Chapters VII specify

a Leve• i analysis

scheme

along with a description of the analysis

for each of the sample

types described.

These three chapters
are entitled:

Analysis

of Inorganic

Materials,

Analysis

of Organic

Materials, Particulate Morphology

and Identification,

and Biological

Testing.

The schemes identify

the methods

of analysis,

anticipated

output

and. predicted level of effort

required

to implement

each analysis

scheme. This manual

also identifies

the ancillary

process

data required

to estimate mass emission

rates,

emission

rates per unit of products

or other calculations necessary

for an environmental

assessment.

The accuracy requirements are consistent

with the Level I environmental

assessment philosophy.This manual

has been made as specific

as possible,

although

it is recognized that it is impossible

to specify

the exact sampling

and analysis procedure for every possible

circumstance.

When situations

arise where alternative Level l sampling

and analysis

procedures

are necess.ary

or desired, the contractor

is directed

to submit

his alternate

plan to his project officer

and the Process

Measurements

Branch,

IERL-.RTP,

Research Triangle Park, for approval

before

actual

work is initiated.

xIvCHAPTER I STRATEGY AND GENERAL

INFORI•ATION The Process

Measurements

Branch

of IERL/RTP

has developed

athreetiered or phased

approach

to performing

an environmental

source

assessment. In this phased

approach,

three distinctly

different

sampling

and analytical activities are envisioned.

While each of the three phases

is briefly

described in Section

1.1, this procedures

manual

focuses

on the Level isampling•and analysis

effort. This manual

describes

for an experienced

professional

a set of sampling and analytical

procedures

which are compatible

with the information

requirements of a comprehensive

Level I environmental

assessment.

This manual

is not intended

for use by inexperienced

personnel.

A comprehensive

environmental assessment

involves

multimedia

environmental

source

sampling.

The techniques described

in Chapters

II through

VI will provide

an adequate sample of fugitive

air and water emissions,

ducted

air and water emissions, liquids and slurries,

and solids

for the analyses

described

in Chapters

Vll through X. The overall

sampling

and analysis

effort

is designed

to be quantitiative in nature

with an overall

accuracy

of a factor

of ±2 to 3.
I.I DEFINITION

OF STRATEGIES The phased

sampling

and analytical

strategy

was developed

to focus available resources

(both manpower

and dollars)

on emissions

which have a high potential

for causing

measurable

health

or ecological

effects,

and to provide comprehensive

chemical

and biological

information

on all sources of industrial

emissions.

Discussions

of this philosophy,

theinformationcost benefits,

and a summary

of the application

of the phased

approach

to sampling and analysis

follow. 1.1.1 The Phased

Approach
The phased

approach

requires

three separate

levels

of sampling

and anal•tical effort.

The first level utilizes

quantitative

sampling

and analysis procedures

accurate

within

a factor

of 2 to 3 and: I) provides preliminary environmental

assessment

data, 2) identifies

problem

areas, and 3) formulates

the data needed

for the prioritization

ofenergy and industrial

processes,

streams

within

a process,

components

within a stream,

and classes

of materials

for further

consideration

in the overall assessment.

The second,

Level 2, sampling

and analysis

effort, after having

been focused

by Level 1, is designed

to provide

additional information that will confirm

and expand

the information

gathered

in Level 1. This information

will be used to define

control

technology

needs and may, in some cases,

give the probable

or exact Cause of a givenproblem. The third phase,

Level 3, utilizes

Level 2 or better

sampling

and analysis methodology

in order to monitor

the specific

problems

identified in Level 2 so that the critical

components

in a stream

can be determined exactly as a function

of time and process

variation

for control

device development. 1.1.2 Strategy

of the Phased

Approach The phased

approach

recognizes

that it is impossible

to prepare

for every conceivable

condition

on the first sampling

or analysis

effort.

In

some cases,

unknown

conditions

and components

of streams

will result

in unreliable information

and data gaps that will require

a significant

percentage of the sampling

or analysis

effort

to be repeated. There is a possibility

that many streams

or even the entire

installation may not be emitting

hazardous

substances

in quantities

of environmental significance. Conversely,

certain

streams

or sites may have such problems that a control

technology

development

program

can be initiated in parallel

with a Level 2 effort.

If either

of these situations

coulld be determined by a simplified

set of sampling

and analysis

techniques,

considerable savings

could result

in both time and funds. A second

possibility

is that budgetary

limitations

may require

prioritizing a series

of installations

so that the available

funds can be used in assessing

those installations

most in need of control

technology.

Here again, a simplified

sampling

and analysis

methodology

would be advantageous to the overall

environmental

assessment

effort.

2The phased

approach

offers

potential

benefits

in terms of the quality of information

that is obtained

for a given level of effort

and in terms of the costs per unit of information.

This approach

has been investigated and compared

to the more traditional

approaches

(Ref. i)and

has been found to offer the posibility

of substantial

savings

in both time and funds required for assessment. The three sampling

and analysis

levels

are closely

linked

in the overall environmental

assessment

effort.

Level I •dentifies

the questions that must be answered

by Level 2, and Level 3 monitors

the probl:ems

identified in Level 2 to provide

information

for control

device

design

anddevelopment. For example,

if a Level I test indicated

that polycyclic

organic material (POM) might be.present

in significant

amounts

and gave a positive mutagenicity test, Level 2 sampling

and analysis

wouldbe

designed

to determine the exact quantities

of organic

constituents,

the percentage

of POM, and the identity

of as many specific

POM compounds

present

aseconomically possible.

In addition,

using the Level I data and any available Level 2 results,

the sample

would be retested

for cytotoxicity

andmutagenicity in order to confirm

and expand

the total bioassay

information.

A test for carcinogenicity

would also be run if the results

of these tests

are positive.

The entire

data package

could then be used to design

the control technology

research

and development

needs for the stream

in the Level 3 effort. A detailed

explanation

of Level i and Level 2 sampling

and analyses along with their expected

outputs

is given in the following

sections. Because Level 3 sampling

and analysis

is totally

process-and

evensitespecific, neither

a general

approach

nor sampling

and analysis

methodolo• gies can be specified

and for this reason,

Level3

will not be discussed further.1.1.2.1 Definition

of Level 1Samplin•

and Analysis The Level 1 sampling

and analysis

goal is to identify

the pollution potential of a source

in a quantitative

manner

with a target

accuracy

factor of ±2 to 3 (0.3).

At the initiation

of an environmental

assessment, little is known about the specific

sampling

requirements

of a source

both practically and technically,

and hence the emphasis

is on survey

tests.
3For

this reason,

no special

procedure

is employed

in obtaining

astatistically representative

sample

and the chemical,

physical,

and biological

testing has survey

and/or

quant.itative

accuracy

•onsistent

with thecharacteristics of the sample. At this level,

the sampling

and analysis

is designed

to show within broad general

limits

the presence

or absence,

the approximate

concentrations, and the emission

rate of inorganic

elements,

selected

inorganic anions, and classes

of organic

compounds.

The particulate

matter

is further analyzed through

size distribution

as well as microscopic

examination

in order to determine

gross physical

characteristics

of the collected

material. Biotesting is designed

to obtain

information

on the human health

effects and biological

effects

of the sample. The results

of this phase are used to establish

priorities

foradditional testing

among a series

of energy

and industrial

sources,

streams within a given source,

and components

within

streams.

Level I has as its most important

function

the focusing

of sampling

and analysis

programs

on specific streams

and components

for the Level 2 effort.

It delineates specific sampling,

analysis

and decision-making

problem

areas,

and directs and establishes

the methodology

of the Level 2 effort

so that additional information needs can be satisfied.

If it can be proven

that equivalent Level 1 data exist for all streams

of interest,

then a Level 1 effort need not be conducted.

If partial

data exists,

Level 1 must be performed

on all streams. Another possible

exception

to the strict

adherence

to the Level I technique involves

the application

of slightly

more sophisticated

procedures where specific

pollutants

of high current

interest

are concerned. In this case, the approach

would involve

a more complex

Level 2 sampling and/or analytical

strategy

in the initial

Level 1 plan.

1.1.2.2 Definition

of Level 2 Samplin•

and Analysis The Level 2 sampling

and analysis

goal is to provide

definitive

data required in the environmental

assessment

of a source.

The basic questions to be answered

and major problem

areas have been defined

in Level I for maximum cost and schedule

efficiency.

Consequently,

Level 2 sampling

andanalysis is characterized

by obtaining

statistically

representative

samples,
accurate stream

flow rates,

and by identification

and quantification

of specific organic

species

and/or

classes

and inorganic

elements

and/or species. Biotesting

in selected

areas is expanded. Although Level 2 sampling

and analysis

require

the use of methodology considerably more complex

than that used in Level I, it will not always be true that a Level 2 effort

at a given site will be more manpower

intensive than the Level 1 effort.

In many cases,

the Level 1 effort

will so thoroughly delineate

the streams

and components

of these streams

of interest that the Level 2 effort

may be less costly

than the Level 1 effort.

Some possible cases are:

• A flue gas source

where volatile

organic

components

were the only materials

.found in a sample

which were ofenvironmental interest;

thus additional

samples

would be needed for complete

analysis.

The additional

samples

could be taken using a simple

organic

sampling

train operated

by one man out of a Car instead

of the SASS train operated

by a crew from a van. A source

where the only stream

of interest

is an ash or refuse stream

with significant

leachable

inorganic

elements of environmental

interest.•

On Level 2, arepresentative sample

would be taken and accurately

analyzed only for the elements

of interest.

A fugitive

emissions

problem

which can be defined

byconventional instruments

and a meteorological

station

operated from a conventional

van. A source

emitting

Particulate

matter

of which only one or two size fractions

are significant

or of interest

for either organic components

or specific

trace inorganic

elements. A source

that only has a water problem,

and either

organic components or trace inorganic

elements

must be analyzed

and the stream

monitored

for accurate

flow rates. A source

where trace inorganic

elements

are found atgenerally low enough

levels

where they are not of environmental significance. The fuel or other raw materials

may be monitored to establish

that the inorganic

constituents

are never input at levels

high enough

to cause an environmental problem. Level 2 would thus provide

sufficient

detailed

information

concerning the problems

delineated

by Level 1 such that control

stream

priorities, 5total environment

insult,

and an initial

estimate

of process/control

system regions of overlap

can be established.

1.2 MULTIMEDIA

SAMPLING

PROCEDURES The Level I procedure

described

in this manual

can be utilized

to acquire process

samples,

effluent

sampleS,

and feed stock samples.

The Level 1 environmental

assessment

program

must, at a minimum,

acquire

a sample fromeach

process

feed stock stream,

from each process

effluent stream, and of fugitive

air/water

emissions.

The feed streams

data are necessary to establish

a baseline

for comparison.

The effluent

stream sampling program

is required

to determine

the mass emissions

rate and the environmental..insult which will result.

Sampling

and analytical

procedures which are required

to support

in comprehensive

environmental

source assessment

must be multimedia

in nature.

1.2.1 Classification

of Streams

for Sampling

Purposes The basic multimedia

sampling

strategy

shown in overview

form in Figure 1 has been organized

around

the five general

types of sampling

found in industrial

and energy

producing

processes

rather

than around

theanalytical procedures

that are required

on the collected

samples.

Thisfacilitates the complex

and difficult

task of organizing

the manpower

andequipment necessary

for successful

field sampling

and establishing

meaningful units of cost.The five sample

types are:

• •as/Va o•_•- These are samples

for light hydrocarbon

and inorganlc gas analysis,

They include

samples

from input and output

process

streams,

process

vents,

and ambient air.

o Liquid/Slurry

Streams

Liquid

streams

are defined

as those containing less than 5 percent

solids.

Slurries

are defined as those containing

greater

than 5 percent

solids.

Nonflowing pastes

are considered

solids.• Solids

-These

include

a broad range of material

sizes from large lumps to powders

and dusts,

as well asnonflowing wet pastes.

Because

the distinction

between

Solids and slurries

can become

blurred,

the reader

should

Consult both Chapters

V and Vl when in doubt.

• Particulate

or Aerosol

Samples

-This

involves

sampling

in contained streams

such as ducts or stacks.

• Eu•itive

Emissions

-These

are gaseous

and/or

particulate emissions from the overall

plant or various

process

units. Flow diagrams

which show the overall

relationship

of the samples

to the analysis

scheme

are shown in Figures

2 and 3. 1.2.2 Phased

Approach

Sampling

Point Selection

Criteria The selection

of sampling

points

in processes

where phased

level sampling techniques

are employed

relies

on the concept

previously

stated: that Level 1 sampling

is oriented

towards

obtaining

quantitative

data with relaxed accuracy

requirements

for determination

of the pollution

potential of a source,

whereas

Level 2 sampling

is intended

to acquire

more accurately the data necessary

for a definitive

environmental

assessment

on prioritized streams. Stream

parameters

such as flow rates,

temperature,

pressure,

and other physical-characteristics will be obtained

on both levels

within

the accuracy requirements

of a given level of sampling.

For example,

a Level 1 particulate matter

sample

is obtained

at a single

point under pseudoisokinetic conditions. This means that the sample

is acquired

at the point of average velocity which has been determined

by a velocity

traverse

taken at typical points in the stream.

The sample

is withdrawn

by means of,a flow rate through the SASS Train Cyclones

(see Chapter

Ill) by using a probe nozzle

which is specifically selected

for isokinetic

conditions;

however,

this flow rate must not be allowed

to change

since a change

in flow rate will alter the particle cutoff

efficiency

of the cyclone

system.

In Level 2, however, where quantitative

data are required,

isokinetic

samples

must be withdrawn using a full traverse

with a port in specific

locations

away from ducting bends and other obstructions

in order to ensurea

sample

representative

of the actual

effluent.

The recommendations

in this manual

are restricted to Level 1 sampling

and analysis

criteria

only.

8INORGANICS ELEMENTS AND

LCA•/MS

SASS TRAIN

[NORGANICS

ABSORPTION IMPINGERS.•,.RACTION I-'•E OIIGANICS

][IN•Ih•II•CMRAiCS•I•AI•AsTION

SAME AS ABOVE

ON-SITE GAS INORGANIC CHROMATOGRAPHY

OR (GRAB) APPROVED ALTERNATIVE

•-,[ EXTRACTION

]•

PHYSICAL SEPARATION INTO 8•CLASSES SEE CHAPTER X.•LIQUOT FOR GAS

PHYSICAL SEPARATION LC/IR/MS INTO FRACTIONS,

Figure 2. Basic Level 1 Sampling

and Analytical Scheme for Particulates

and Gases

9LEACHABLE MATERIALS ORGANICS

BIOASSAY SEE CHAPTER X

QA PHYSICAL SEPARATION INTO FRACTIONS

LC/IR/MS
ELEMENTS AND SELECTED ANIONS

SOLIDS

SOLID/LIQUID

LIQUIDS INORGANICS

ELEMENTS AND SELECTED ANIONS PHYSICAL SEPARATION INTO FRACTIONS ORGANICS LC/IR/MS INORGANICS

ELEMENTS AND SUSPENDED NIONS SOLIDS ORGANICS BIOASSAY SEE CHAPTER X

INORGANICS ELEMENTS AND SELEaED ANIONS
SELECTEDWATER SEE• SECTION 7.2.6 TESTS CHAPTER (AQUEOUS)

ORGANICEXTRACTION OR DIRECTANALYSIS

ORGANICS

EHYSICAL SEPARATION INTO FRACTIONS >CI2 LC/IR/MS

ORGANICS ALIQUOT FOR GAS CHROMATOGRAPHIC <C12 ANALYSIS

Figure 3. Basic Level 1 Sampling

"and Analytical

Scheme for Solids,

Slurries

and Liquids

10Similar considerations

apply to site Selection

for sampling

liquids and solids.

On Level 1, liquid

samples

can be taken from tanks or other container• without

depth •integration

and from pipes using a simple

tap sample rather

than using a multiported

probe to take a time integrated sample. In slurry

streams,

an effort

should

be made to sample

a turbulent

or well mixed area, but this and other requirements

can berelaxed

considerably for Level I site selection. In the case of solids

sampling,

the standard

procedures

used insampling piles and stationary

containers

are relaxed

on Level 1 both by taking fewer increments

to make a composite

and by relaxing

or eliminating

the requirements for depth integrated

sampling.

For moving

solid streams,

a simplified sample

is obtained

by reducing

or eliminating

the number

of increments required

for the time averaging

aspect

of the s•mplingprocedure. in most cases,

Level 1 sampling

method•

generally

encompass

approved standard EPA, ASTM, and API techniques.

Modifications

are then made to these techniques

to adapt them to the time and cost constraints

consistent with the Level 1 sa•ling

philosophy.

These modifications

include: i) reducing

port selection

criteria;

2) eliminating

the requirements

for traversing, continuous

isokinetic

sampling,

and.replicate

sampling

in the collection of particulate

matter;

and 3) use of grab samPles

for ambient, water, and solid samples.

Using these sampling

point selection

criteria,

a sampling

point selection

model illustrating

Levels

I and 2 sampling points as developed

in another

program

(Ref. 1) is shown in Figure

4 for a wet limestone

spray tower system

installed

at Paducah,

Kentucky. 1.2.3 Stream

Prioritizat•on

Using the Phased

Approach Industrial and energy

producing

processes

are highly

complex

systems consisting of a wide variety

of interrelated

components.

Level 1 sampling will show that many influent

and effluent

streams

have no environmentally significant impact.

These data can be used to reduce

the number

of samples required for Level 2 substantially,

and can permit

reallocation

of resources. Thus, comprehensive

stream

prioritization

based on the Level 1 sampling and analysis

effort

will identify

streams

with widely

varying

environmental priorities. In many cases,

the Level 1 information

will be sufficient

to

11eliminate certain

streams

entirely

from the Level 2 effort,

In other cases, limited resources

may require

the omission

of Certain

low priority

streams. 1.3 DATA REQUIREMENTS

AND PRE-TEST

PLANNING

(Ref. 1, 2, 3, 4, 5, 6)
The final decision

to test a particular

plant will be the result

of the prior•tization

studies

and of the preliminary

selection

process

based

on the site selection

criteria

of a given program,

and on the datarequirements of the overall

program

or general

EPA objective. Before the actual

sampling

and analysis

effort

is initiated,

the data requirements must be established

and used to help identify

testrequirements as well as any anticipated

problems.

The following

paragraphs

present a general

summary

of these requirements

and planning

function

which must be applied

or expanded

to meet the needs of the individual

tests to be performed.

Specific

recommendations

concerning

data requirements

associated with each of the process

streams

are discussed

in the appropriate chapters of this manual. 1.3.1 Process

Data Needs Before traveling

to a plant for a pre-test

site survey,

it is necessary to become

familiar

with the process

used at the site.

This involves understanding the chemistry

and operational

characteristics

of the various unit operations

as well as any pollution

control

processes.

It isparticularly important

to know that detailed

relevant

process

data are necessary for the sampling

and analysis

effort

as well as for the overall

environmental assessment.

The reasons

for this are: 1) From a knowledge

of the process

and the composition

of input materials

and products,

conclusions

about pollutants likely to be found in waste streams

can be drawn 2) One must know where to look for waste streams,

including fugitive emissions 3) One must know how plant operating

conditions

are likely to affect

waste stream

flow rates and compositions 4) Thorough

familiarity

with the process

permits

design of a proper

sampling

programs

135) Thorough

knowledge

of the interrela•ion•k-•mo• process variables

permits

extrapolation

toconditions in other sizes of the system

being assessed, and6) Detailed

process

data are the basis from whichcontrol technology

development

programs

proceed,

should environmental assessments

indicate

such need. Familiarization with the process

is also necessary

so that a checklist

of the requisite

data can be developed,

including

temperatures,

pressures, flow rates,

and variations

of conditions

with time for the pre-test

site survey.For any given sampling

and analysis

task, the data collected

must be consistent

with the overall

Level I objectives.

Thus, the minimum amount of data for a given stream

is flow rate per unit time at a given temperature and pressure.

Additional

data that may be necessary

are average flow per unit time, the effect

of process

variations

on stream flow and composition.,

and normal

variations

in flow and compositions

with variations in process

cycling.

Appendix

A contains

a checklist

ofappropriate data that may be collected.

It is expected

that professional sampling and analysis

personnel

in conjunction

with the EPA Project Officer and PMB-!ERL-RTP

will select

the appropriate

data requirements

for
a given industry. 1.3.2 Pre-test

Site Surve• After establishing

the necessary

process

data needs and selecting

a tentative set of sampling

points,

a pre-test

site survey

should

beperformed. At the test site, the survey

team should

meet with the plant engineer to verify

the accuracy

of the existing

information

and arrange for the addition

of any •issing

data•

Using this information,

the survey team will then proceed

to select

the actual

sampling

sites with thefollowing criteria

in mind: The sampling

points

should

provide

an adequate

base of data for characterizing

the environmental

impact

of the source on the environment

within

a factor

of 2 to 3. When possible,

each sampling

point should

provide

a representative sample

of the effluent

streams.

(This is a desirable

but not a strict

requirement

of Level I sampling).o The sampling

site must have a reasonably

favorable working environment.

The Survey

personnel

mustconsider the temperature

and noise level in the sampling areas, if protection

from rain or strong

winds exists, and whether

safe scaffolding,

ladders,

pulleys,

etc.,
are present. The identification

of support

facilities

and services

is an essential aspect of the site survey.

In an effort

to minimize

the requests

made upon the operators

and scheduling

problems

for these support

services, it is desirable

that the test van operate

completely

independently

of external support

facilities.

The large electrical

power requirements

of the test van and th• sometimes

limited

electrical

power availability

at many industrial/commercial sites make it important

that the van carry sufficient electric

generating

capacity

to operate

all test and support equipment. The van should

also carry a water tank for essential

services. Where available,

electrical

power and water services

may be connected

for auxiliary service.

These and other specific

mobile

laboratory

fabrication requirements for Level 1 Sampling

and analysis

are presented

in Appendix

B. The results

of the pre-test

site survey

must be sufficiently

detailed

so that the field test problem

of sampling

the correct

process

stream at the proper

sampling

location

and using the appropriate

methodology

will be completely

defined

prior to arrival

of the field test team at the source site.1.3.3 Pre-test

Site Preparation Since in most cases the manpower

requirements

for site preparation

are usually low to moderate,

a relatively

low effort

was assumed

for site preparation, under the assumption

that major modifications

required

in extreme cases are out of the scope of this manual. Thus, it was assumed

that the erection

of scaffolding

and the provision of power will be a major part of site preparation;

a further

assumption

was that the required

manpowerwill

be associated

to a large eXtent

with stack sampling, the most complex

sampling

procedure.

Preparation

of other sites

was assumed

to be minimal

and/or

part of the actual

sampling

procedure. The installation

of special

samplers,

valves,

fittings,

etc. is considered beyond the scope of a Level 1 sampling

effort..

151.4 ANALYSIS

OF.SAMPLES Chapters Vll through

X specify

analysis

schemes

and procedures

that will provide

data relatable

to all existing

EPA standards

and thoseadditional data requirements

specified

above for Level 1 environmental

assessment. These schemes

identify

accepted

methods

of analysis,

anticipated output, and the estimated

level of effort

required

to im•lemen•

theanalysis scheme.There

are seven categories

of analysis:

• Organic

Analysis

Survey

techniques

are used to identify compound

classes

by functional

group.

• Inorganic

Element

Analysis

Based on spark source mass spectroscopy

(SSMS) which can perform

a general survey of all effluent

streams

for possible

inorganic elements.

• Particulate

Morphology

Inaludes

microscopic

examination of shape,

size distribution,

surface

features and possible

source.

• Water Analysis-

Reagent

test kits will be used as
a supplement

for those analYses

that are•not

covered by SSMS or organic

analysis.

• Gas Chromatographic

Analysis

Consists

of On-site

analysis of gaseous

and/or

low boiling

organic

and inorganic s•ecies.

• Opacity-

This test will be performed

using a simple Ringelmann Chart.

• Bioassay

Testing

Includes

selected

health

and ecological testing

on all solid and liquid

samples, and is designed

to measure

the environmental

and health effects

potential

of a given source

stream

in
a broad and general

manner.Fable 1 shows the recommended

sample

volumes

that must be collected which will result

in the listed

sensitivities

when the recommended

analysis method

is used.

These sensitivitieshave been selected

by PMB-IERL-RTP for both inorganic

and organiccomponents so that all species

Of current interest can be analyzed

at levels

which at present

are the lower limits of environmental

concern. 1.5. ACCURACY

AND PRECISION

OF RESULTS
The accuracy

and precision

requirements

for a Level 1 environmental assessment have been discussed

in general

terms as being quantitative

within

a factor

of ±2 to 3. In general,

most of the sampling

and analysis

procedures which have been

selected

for this Level 1 manual

are adaptations

of standard EPA, ASTM, API, etc., methods

which have a accuracy

and/or

precision factor

of ±10-20

percent

or better.

These requirements,

however, have been reduced

to fit the .economic

and philosophical

constraints

for a Level 1 environmentalassessment. In order to determine

emissions

from a given site to within

a factor

of 52 to 3, both the sampling

and analytical methods must have a precision

which is better

than a factor

of 2. Thus, if the sampling

parameters

for a given sample

along with the corresponding

analyses both had a precision

within

a factor

of 2, then the overall

precision

cam be calculated

on the basis of equation

(i).

2 •tota] •/•sampling

+ •nalysis eq.(1)

Then, if x were the true value,

and the

precision

limits

for both sampling and analysis

are within

a factor

of 2.0, the individual

values

would range from O.SX to 2X. Substituting

these values

into equation

(1) gives a range from O.3X to 3.8X for the precision

of the final value which is to be used for the environmental

assessment.

(For the lower limit Otota I = X •0..•=

O.3X and for the upper limit,

•total

X +•8X 2 3.8X).

17Table I. Recommended

Sample

Sizes and Detection

Limits Sample Source Sample

Type

Inorganic

Organic Stack 30m3

3(1,06Oft)

Gas d) 3 liters

Ambient Air 480m 3a)(17,00Oft 3) Liquid 10 liters(2.5 gal)
Solid I kg(2.2 Ib)

a)' Particulate

Matter

O.01ug/m

3 2•g/m 3lOug/m 3
General Components,

1 mg/• 3e) lO0pg•m

3f) •I Sulfur

Compounds

g)

l•g/m j

1•g/mJ
Particulate Matter

O.01pg/m•

30•g/• 3 a)b) Sorbent

Trap, >C12

O.01,g/m•

l•g/mJ• c) Sorbent

Trap, •6-C12

O.01•g/m

j lO•g/m j lpg/l h) 10•g/l

1 mg/g

100 ng/g
a)b)c)
d)
f)g)h) At STPThe analysis

is terminated

for organic

material

if less than 15 mg (0.5 mg/m 3) of organic

components

are extracted

from the total sample.
Assumes that the XAD extract

is 2 liters

and a 1 •l sample

is injected into a G.C. with a flame ionization

detector

with a 0.1 ng detection limit.A maximum

sample

•ize of 10 ml is assigned

for all cases. Detection limit is approximately

1 ppm. Detection limit is approximately

0.1 ppm. petection limit is approximately

1 ppb. Assuming a 0.1 ml sample

for SSMS electrode

formation

and a lO-9g instrument sensitivity.

18From this explanation,

it can be seen that when it is stated

that results are accurate

with a factor

of three,

it means that actual

va•ue may lie in a range from 1/3 that value to more than 3 times the value. It should

be noted that this is a target

accuracy

and that some procedures may easily

meet these criteria

while for others,

it may be a slightly optimistic.CHAPTER II GAS AND VAPOR SAMPLING

METHODOLOGY
2.1 INTRODUCTION

References

I, 3, 4, 7, 8, 9, 10) This chapter

discusses

the general

methodology

for obtaining

gaseous samples for analysis.

Obtaining

a representative

sample

from a simple gaseous stream

can be complicated

by stratification

from incomplete

mixing
or by variations

in stream

components

over a period

of time.

For thepurpose of Level 1 assessment,

a single

grab sample

is sufficient,

although planning is necessary

to ensure

that sample

acquisition

is made at a reasonably representative

point (position

and time) in the stream

orprocess cycle (see Chapter

I). This chapter

discusses

the sampling

methodologies

applicable

to the following stream

types:

• Process

streams,

vents,

and effluents.

• Fugitive

gaseous

emissions. Gaseous process

streams

refer to contained

gases being transported from one area to another.

These streams

exist under conditions

which range from a slightly

negative

pressure

to highly

pressurized

pipeline

systems. Also, the contents

of gaseous

process

streams

range from corrosive

and toxic process

effluents

to complex

organic

mixtures.

For the purposes

of source assessment,

only those internal

streams

which process

influents

and effluents to the environment

are considered

for sample

acquisition.

Consequently, internal

process

streams

are seldom

of concern

since they do not constitute

influents

or effluents

in contact

with the environment. Exceptions to this rule involve

such streams

existing

prior to control devices or which are held for interim

periods

prior to discharge,

such as holding or surge systems

situated

in-line

prior to flare discharge. Gaseous process

vents are generally

found in tank farm areas or in various system

operations

requiring

pressure

surge variability. Gaseous process

effluents

refer to ducts or flues which are exhausted to the atmosphere

and for the purposes

of this chapter

only the CI-C 6

20and

inorganic

gaseous

effluents

from these units are considered.

The particulate content

along with higher

molecular

weight

hydrocarbons

are obtained via the Source

Assessment

Sampling

System,

which is discussed

in detail in Chapter

III. FuBitiv e Baseous

emissions

result

from various

process

leaks such as those found in pumps,

valve seals,

ducting

or process

connections

and the open transfer

or storage

of liquid

process

raw materials,

intermediates, and products. 2.2 SAMPLING

TEST PREPARATION

(References

I, 3, 4) Complex process

operations

represent

diverse

conditions

which require careful planning

of the sampling

activity.

This planning

should

be based

on data compiled

from actual

plant records

or from plant personnel

familiar with the characteristics

of each sampling

location.

A pre-test Level I site survey

of process

streams

and vents for sampling

g•seous

components involves

the following

six steps: I) Obtaining

detailed,

accurate

process

flow diagrams.

They should be as current

as possible

and can be updated

and supplemented by conversations

with plant personnel. 2) Tracing

the process

flows to establish

gaseous

outputs. Using the process

flow diagrams

as a guide,

a physical inspection of the systemmust

be conducted

to uncover

any undocumented output

sources

or unrecorded

equipment modifications. 3) Locating

and itemizing

process

vents. 4)s) Locating

and itemizing

stacks

and flares. Selecting representative

sites.

The goal of Level 1 sampling is to uncover

any pollution

sources

and to quantify the emission

levels within

a factor

of ±2 to 3. If, in this sense,

toxic materials

arediscovered, then a fu11-scale

Level 2 analysis

will be initiated to quantify

the problem.

Thus, theselection of representative

Level l sampling

sites should reflect this philosophyof

obtaining

the type of a sample for analysis

rather

than typical

compliance testing criteria.6) Recording

the physical

parameters

of the stream

in as much detail as possible

to facilitate

the sampling

effort

and to aid in post-sampling

data reduction.

Specific

guidelines regarding

parameters

of interest

may be found in Appendix B. Aside from these genera]

considerations,

there are two specific

requirements for gas and vapor sampling: i) All process

streams

and vent systems

recirculated

into process streams

will require

in-line

valves

for sampling. .2) All vents to the atmosphere

require

a means of access as well as suitable

working

space for personnel involved in the sampling

process. 2.3 GAS SAMPLING

TECHNIQUES

(References

11, 12, 13, 14, 15,

161, 17, 18) As stated

in Section

2.1, a single

grab sample

of each stream

in question is sufficient

for Level I needs.

The grab sample

may be taken in one of three ways, depending

on the pressure

of the stream

in question. These three grab sample

types are high pressure

line, grab purge and evacuated grab samplers,

and are illustrated

in Figures

5, 6 and 7 respectively. 2.3.1 High Pressure

Line Grab Samples The apparatus

illustrated

in Figure

5 is used when the pressure

is high enough

in the stream

to require

a side-split-bleed to provide

asufficient pressure

reduction

for effective

bulb purge.

The •ampling

bulb is the dual valve positive

displacement

type aBd is 3 liters

in volume. The bulb must be purged

with approximately

tem volumes

of the stream gas before

the sample

is isolated. A smali glass wool plug is inserted

in-line

prior to sampling

to prevent the influx

of particulate

matter

into the bulb during

the purge and sample

collection

periods.

222.3.2 Slight

Positive

Pressure

Grab Purge Sampling The positive

displacement

dual valve glass sampling

bulb described above may also be used in ducts,

pipes or vent systems

where linepressure is slight.

Since the pressure

is slight,

however,

a side-bleed

is not required

for pressure

reduction.

Figure

6 shows the apparatus

configuration for this sampling

method."

A small glass wool plug is inserted in-line before

sampling

is begun,

and approximately

ten volumes

of sample gas must be purged

through

the bulb prior to isolation

of the sample. 2.3.3 Negative

Pressure

Evacuated

Bulb Sampling Figure 7 illustrates

the sampling

bulb used for sampling

negative pressure systems

or open effluent

lines such as vent systems

or point fugitive emissions

(the latter

are discussed

in Chapter

IV). The bulb is also 3 liters

in volume;

however,

it is the single valve evacuated

type rather

than the dual valve positive

displacement type. The number

of bulbs required

for a given sampling

effort

will be known as a result

of the pre-test

site survey

(Section

2.2).

The bulbs
are then evacuated

in the field using a small vacuum

pump from the mobile
van or trailer.

The evacuated

bulbs are then taken to their respective sites for sample

acquisition. The entrance

nozzle

of the bulb must be fashioned

so that a piece of tubing can be attached.

The tubing

acts as a probe to be inserted

into either the duct or vent and should

be made from I/4 inch OD Teflon

tubing 12 inches

in length. The tube attached

to the evacuated

bulb is inserted

into the vent or negative pressure

duct and the sample

is withdrawn. 2.3.4 General

Considerations For safety

reasons,

all of the above described

sampling

bulbs must be encased

in a protective

jacket

of styrofoam. Cleaning of the containers

is especially

important

in order toprevent contamination

of samples.

New glass containers

should

be conditioned prior to use by allowing

them to stand full of distilled

water for several days. This conditioning

process

may be accelerated

by rinsing

thecontainer with dilute

hydrochloric

acid followed

by distilled

water.After use, containers

should

be thoroughly

cleaned.

A 2:11 mix of Alconox or abrasive

cleaner

and water may be used followed

by a tap water rinse. The container

is then rinsed

with a i:1 mixture

of H2SO 4 and HN03, followed

by a tap water rinse of the acid, followed

by a final flush- •ng with three volumes

of high purity

water. Sampling bulbs cleaned

in this way may then be dried,

filled

with nitrogen and stored

until ready for Use. 2.4 SAMPLING

PROCEDURES This section

briefly

describes

the problems

and considerations involved in sampling

process

streams,

fl•ues and ducts,

and vents. 2.4.1 Process

Streams,

Flues and Ducts A prpcess

stream

may require

any of the three previously

described grab sample

types depending

on the nature

of the stream.

A stream

under elevated positive

pressure

will require

the apparatus

described

inSection 2.3.1.

Streams

under only slight

positive

pressures

and streams under negative

pressures

will require

the apparatus

described

inSections 2.3.2 and 2.3.3 r•spectively. Whatever sample

type the process

conditions

require,

the primary issue involves

the careful

planning

needed

for the

selection

of the.most representative sampling

point.

Frequently,

pipeline,

duct and ventsystems consist

of composite

streams

wherein

the main or primary

stream

is joined in one or more places

by secondary

streams.

When this is the case,
a sampling

point must be Chosen

far enough

downstream

of the joint to
ensure component

homogeneity.

An optimum

choice

for sample

withdrawal

in gaseous systems

is at a point downstream

from a bend in the pipe or duct, since a bend induces

turbulence

and therefore

homogeneity. In-!ine valves

or sampling

ports must also be assessed

for their compatability with available

apparatus.

For example,

the process

port
or valve entrance

will in many cases be larger

than the bulb entrance. To solve this problem,

a series

of.one-hole

stoppers

Of various

size increments may be used to fit over the bulb nozzl'e

entrance.

27For the high pressure

(Figure

5) and low pressure

(Figure

6) sample collection, all sample

containers

must be purged

with approximately

ten volumes of the sample

gas prior to collection

of the sample

(•his should take approximately

2 minutes).

For the subatmospheric

pressure

(Figure

7) sample collection,

the sample

should

be collected

by slowly

cracking

the valve and letting

the sample

bleed in (approximately

30 seconds). 2.4.2 VentsVent systems

generally

consist

of relief

tubes or exit.ducts

regulated by in-line

pressure

release

valves.

Vents are found in holding tanks and storage

tanks and are usually

discharged

into the air when the tank pressure

exceeds

the pressure

setting

of the in-line

valve.

The velocity of the gases being emitted

from vent systems,

as well as the time duration of the vent cycle,

is directly

proportional

to: 1) The diameter

of the vent tube, 2) The headspace

volume

of the system

being vented.,

and 3) The pressure

setting

of the in-line

relief

valve. Units or tanks with pressure

vent releases

to ambient

air are sampled with a 3-1iter

evacuated

bomb (Figure

7). The important

considerations

in obtaining vent gas samples

are:

• The sample

must be taken whi|e the vent cyc|e is in pro• gress. (Cycle periods

for individual

processes

should be known as a result

of the pre-test

survey).

• The entrance

nozzle

of the bomb should

be situated

so that a representative

sample

of the vent effluent

is obtained without

contamination

by ambient

air. 2.5 SAMPLE

HANDLING

(References

3, 14• 15) All gas samples

described

in this chapter

will be analyzed

by gas chromatography using procedures

described

in Chapters

VII and VIII. Because many streams

contain

components

which will interact

with one another, it is .important

that the sample

be delivered

to the mobile

unit

as soon as possible

to avoid significant

alteration. Glass sampling

bulbs must be encased

in styrofoam

protectors

to avoid breakage and possible

injury

to members

of the sampling

team.CHAPTER III GASEOUS STREAMS

CONTAINING

PARTICULATE

MATTER 3.1 INTRODUCTION Stationary

source

particulate

matter

sampling

and analysis

have been restricted to streams

of high mass loading

because

the sampling

flowrates of the sampling

equipment

have not been high enough

to collect

an adequate amount of material

in a reasonable

length

of time (Ref. 3, 6, ]9). In addition, healtheffects

data indicate

that an adequat

e assessment

of the collected particulate

matter

requires

size fractionation

into at ]east four size fractions

(Ref. 6• 20). Also, provision

must be made for the collection of volatile

trace elements

and organic

species.

For all of these reasons,

the EPA (IERL-RTP)

has developed

and specified

the use of the Source

Assessment

Sampling

System*

(SASS)

train (Figures

8, 9 and lO) for the collection

of particulate

and volatile

matter

in addition

to the gaseous samples

discussed

in Chapter

II. The sampling

train consists

of a stainless

steel probe which enters an oven module

containing

3 cyclones

and a filter.

Size fractionation

is accomplished in the series

cyclone

portion

of the SASS train, which incorporates the cyclones

in series

to provide

large quantities

ofparticulate matter

size-classified

into three ranges:

a) >lO •m, b) 3 •m to lO •m, and c) •m to 3 •m. Together

with a standard

142 mm filter,

a fourth

cut, <l •m is obtained.

Volatile

organic

material

is collected

in a XAD-2 sorbent trap.

The XAD-2 trap is an integral

part of the gas treatment

system which follows

the oven containing

the cyclone

system

(see Figure

8). The gas treatment

system

is composed

of four primary

components:

the gas conditioner, the XAD-2 adsorbent

trap, the aqueous

condensate

collector,

and a temperature

controller.

The XAD-2 sorbent

is a porous

polymer

resin with the capability

of adsorbing

a broad range of organic

sPecies.

Some trapping of volatile

inorganic

species

is also anticipated

as a result

of simple impaction. Volatile

inorganic

elements

are collected

in a series

of impingers. The pumping

capacity

is supplied

by a lO-cfm

high volume

vacuum
Manufactured by Aerother•

Corporation,

485 Clyde Avenue,

Mountain

View, Ca., 94042,

Tele. (415) 964-3200.

29>ZO>'uOZ

3031,32pump,

while required

pressure,

temperature,

power and flow conditions

are obtained from a main controller. A schematic

for flue gas sampling

and analysis,

which forms the basis for this chapter,

is shown in Figure

II. Details

of the sample

handling and transfer

procedures

are presented

in Section

3.5. Knowledge ofthe

size distribution

of particles

emitted

from given industrial or energy

sources

is important

to considerations

of engineering, environmental and health

effects.

In the first instance,

design

and/or evaluation of particulate

matter

control

devices

rely upon these data. Secondly, it may be predicted

that the large particulate

ma•ter

fraction will deposit

inclose

proximity

to the source,

whereas

the fine particulate matter which is more difficult

to control,

will be carried

airborne

for long distances. These minute

particles

can often affect

weather

and visibility and may possibly

modify

the heat balance

of the earth. '3.2 PARTICULATE

MATTER

SAMPLING

METHODOLOGY

(References

4, 15, 21, 22, 23) In normal

research

and compliance

testing,

great care is taken to ensure that isokinetic

conditions

are maintained

and that a proper

traverse is performed.

A Level l sample

is acquired

at the point of average

velocity which is determined

by a velocity

traverse.

The sample:is

withdrawn

at a constant flow rate using a nozzle

which is specifically

selected

forisokinetic conditions

when the testis

initiated.

For the accuracy

requirements of Level l, this flowrate

is allowed

a slippage

of from •30 percent to +50 percent

Of the specified

isokinetic

rate.

Conditions

existing

outside of. the above specified

marginmust

result

in SASS train shutdown

for

an inspection

of the problem.

The cause of the deviation

from isokinetic conditions frequently

may be traced

to cyclic

variations

in grain loadings

or simply

to • continuous

high grain loading

density,

as.well

as an increase/ decrease in gas velocity,

or the inability

of the pump to pull the volume required to meet .particulate

matter

collection

requirements. Two possible

situations

occuring

within

the SASS train will manifest pressure variations

outside

of the acceptable

margin.

They are: I) Clogging

of the probe nozzle,

and 2) Clogging

of the backup

filter.The

only possible

solution

in both cases requires

SASS train shutdown

and concomitant probe nozzle

cleaning

oN filter

replacement. 3.3 PREPARING

FOR SAMPLE

COLLECTION 3.3•I Pre-Site

Survey After performing

the general

site survey

and obtaining

the necessary process data as described

in chapter

I, the survey

personnel

should

select the appropriate

sampling

site with the following

criteria

in mind:

• When possible,

each Sampling

point should

provide

a sample which represents

as closely

as possible

the chemical

composition and mass emission

rate of the effluent

stream.

(This is a desirable but not a strict

requirement

of Level l sampling

as described in Section

1.3 and 3.2).

• The sampling

site must have a reasonably

favorable

working environment. The survey

personnel

will consider

thetemperature and noise level in the sampling

areas,

whether

protection from rain or strong

winds exists,

and whether

safe scaffolding, ladders, pulleys,

etc., are present.

• Having

located

the appropriate

sampling

location,

the physical characteristics of the stream

(temperature,

flow, grain density, etc.) should

be determined

from run engineers.
It is intended

that the results

of the pre-test

site survey

besufficiently detailed,

so that the field test problems

of sampling

the correct flue gas stream

at the proper

sampling

location

and of using the appropriate methodology will be completely

defined

prior to arrival

of the field test team at the source

site.

These data should

be recorded

in the form of a pre-test survey

report. 3.3.2 Personnel

Requirements The personnel

requirements

are related

to the magnitude

of the sampling task; however,

.certain

general

correlations

can be made.

Thesecorrelations can be scaled

in a reasonably

linear

fashion

and then applied

to the sampling task at hand in order to tailor

manpower

and time requirements

to .fit the task (Ref. l, 6, 24). The acquisition

of a Level l sample

using a SASS train generally

requires
two and i.n some cases,

three persons

for equipment

assembly

and disassembly. After assembly

the •rain requires

from one to one and one-half

persons

for operation. The remaining

manpower

is then available

for other on-site efforts. 35Each SASS train run will consist

of approximately

a five•hour

period (specific sample

acquisition

criteria

are described

in Section

3.4).

The number of required

personnel

for this function

will not increase

regardless of the.number

of sample

sites,

provided

that a sufficient

time allotment exists within

the sampling

task to allow for consecutive

sampling. Manpower projections

can then be determined

by considering

the number of SASS particulate

m•tter

•amp1•

•qui•d

t• C-•rac•e••e

the •site in question"• the time required

for the acquisition

of each sample

(determined

as afunction of analytical

objectives),

and the number

of personnel

and/or

samplers available for the task. 3.3.3 Equipment

Preparation

for Sample

Collection The following

sections

discu•s

•.• •p•

prepa•at•onrequi• for the SASS train,

including

cleaning

procedures

of the train components

and sample containers,

and apparatus

checkout.

The SASS train schematic

and

3.3.3.1 Precleanin•

Procedures

for the SASS Train and Sample

Containers (References 3, 4, 6, 25, 45) The SASS train is the•most

complex

sampling

unit discussed

in this manual,

and an overall

generaiiz•d

•ie•ni•g

p•Ocedur•

cannot

beestablished. Two primary

cleaning

methodologies

are required.

The first methodology, described

in this section,

concerns

the technique

involved in producing

biologically

inert surfaces

throughout

the SASS train.

The second methodology,

described

in Section

3.5 (Sample

Handling

and Shipment), presents the techniques

required

for cleaning

or removing

sample

from various parts of the train after the run. The first stage in preparing

the sampling

train and sample

containers for sample

coliection

is prepassivation

with a nitric

acid solution.

All surfaces in the sampling

train which come in contact

with sample,

as well

as all sample

containers

andcontainers

for the impingers,

should

be prepassivated by a one-hour

standing

contact

with l:l (V/v) aqueous

nitric acid. Two separate

approaches

are used for subsequent

cleanings:

one for SASS train components

and organic

sample

receptacles;

and the other for bottles holding

impinger

solutions.

The first group is cleaned

in threesuccessive stages

using a different

solvent

in each stage.

The solvents used are distilled

water,

isopropyl

alcohol

and methylene

chloride,

in the order listed.

This procedure

removes

all extraneous

particulate

matter

and pro-. duces a clean,

dry surface.

As each part is treated

with the final solvent (methylene chloride),

it is purged

dry in a filtered

stream

of air •r dry nitrogen and inspected

throughly

for any sign of contaminating

residue, scale, rust, etc. A contaminated

train component

may •o__•t be used in a sampling run. All equipment

treated

in the above fashion

must be placed in a clean area to await the next test.

Disassembled

components

of the sampling train which trap particulate

matter

are to be draped

withcleanroom grade nylon until ready for use. The bottles

holding

the impinger

solutions

are cleaned

in two successive stages, involving

distilled

water,

followed

by isopropyl

alcohol. The field area in which these cleaning

operations

are performed

must be as clean as possible

under existing

field conditions.

An enclosed

space is required

in which reasonable

precaution

has been taken to remove

spurious dust, dirt or particulate

contaminants.

Reasonable

precaution

is intended to mean that the area has been swept clean,

doors or significant

draft inducing sources

have been closed

and c•earroom

grade nylon has•een spread Over the work bench area. 3.3.3.2 Apparatus

Checkout The following

tasks should

be performed

in the home base laboratory prior to field arrival: I) Gather

together

all components

required

for complete

system assembly. 2) Clean components

in accordance

to the above described procedure. 3) Leak check the entire

system. Besides the cleaning

procedures,

leak checking

the train prior to field use is one of the most important

pre-test

tasks to be performed. This simple

procedure

can save hours of sampling

time in the field.

The leak checking

procedure

involves

sealing.the

probe tip, turning

on the pumping system,

and observing

flow meter gauges

for the existence

of any appreciable flow.

The a11owable

leak rate for the SASS train is 0.05 cfmat

a pressure

of 20 inches

•f Hg. The instructions

accompanying

the train will present

in detail

the steps involved

in,leak

checking

the system. 3.4 SERIES

CYCLONE

SAMPLING

PROCEDURE Assuming that the series

cyclone

system

has been cleaned

in accordance with the specification

presented

in Section

3.3 prior to arrival

at the site and that all process

characteristics

have been determined

and recorded

as outlined above,

a Level I sample

may be taken as follows

(Ref. 6): I) Assemble

sampllng

apparatus

in accordance

with the manufacturer's specifications. 2) Warm up those components

that require

preheating.

These are the probe,

the oven, and the temperature

control

fluid in the XAD-2 Module.

Under most conditions

15 to 30 minutes ar t required

for preheating.

Theoven

and probe should

be maintained at 205oc (400OF).

The temperature

of the cartridge should be kept at 20°C (68OF). 3) ̧4) Measure

the stack temperature,

moisture

content,

and velocity profile. Determine

the position

in the stack which corresponds to the average

stack velocity. Leak test the system.

As mentioned

earlier

in Section

3.3.3.2, the equipment

should

be thoroughly

leak-checked

prior to site arrival. If this has been done properly,

the on-site

leak test should simply

be a precautionary

formality

to ensure

that all fittings are properly

tightened. Using the procedures

and calibration

curves

supplied

by the manufacturer, compute

the appropriate

sampler

flowrate

and the proper nozzle

size. 6) Fill the impinger

bottles

with the reagents

specified

in Table 2.7) Install

the nozzle

on the probe,

and then insert

the probe into the stack or duct.

The nozzle

should

be in the proper posit!on in the duct, as determined

in (3). 8) To initiate

the sampling

run, turn on the vacuum

pump and throttle the intake

valve to achieve

the flowrate

determined in (5). (A 3- to 5-cfm sampling

rate should

be achieved

at the dry test meter.) 9) During

the course

of the run, periodic

checks

and adjustment of flowrates

and temperatures

should

be made.

3BThe quantities

of sample

needed

in order to perform

the required analyses are presented

in Chapter

I (Table

1). Naturally,

the knowledge of whether

or not these quantities

have been acquired

during

the runcannot be obtained

until subsequent

gravimetric

analyses

have been performed. For this reason

the PMB has developed

a series

of sampling

guidelines criteria for acquiring

the required

quantity

of sample

during

each run. These criteria

are:At least one process

cycle and 30 standard

m 3 (1060 scf) of the process

effluent

are-•-•-be

sampled

during

each run. In the event that the process

is not cyclic

in nature, the 30 standard

m3 figure

must still be satisfied

over a period of time conducive

to obtaining

a sample

representative of process

conditions.

A sampling

duration of five hours has satisfied

this requirement

in the past. To fulfill

the above conditions

it may be necessary

on several occasions (due to high grain loading

conditions)

to interrupt

theprogress of the run to change

the filter

or nozzle

due to clogging

problems. This is an acceptable

procedure;

however,

care must be taken to avoidcontamination in the process

of transfer.

A detailed

log should

be kept to record'any relevant

conditions

pertaining

to the change. 3.5 SAMPLE

HANDLING

AND SHIPMENT

(References

3, 4, 22, 25, 26) The procedures

used in transferring

acquired

sample

from various portions of the SASS train are extremely

involved.

To expedite

the explanation of the procedures

involved

in sample

transfer

and handling, the subject

is discussed

in te•ms of a modular

approach.

For this reason, the SASS train is considered

in terms of the following

sections: 1) Nozzle

and probe, 2) Cyclone

system

interconnect

tubing, 3) Cyclones, 4) XAD-2 module, 5) Impingers.At the transportedI) conclusion

of the sampling

run, the train is disassembled

and to the mobile

lab unit Or prepared

work area as follows: Open the cyclone

oven to expedite

cooling,

disconnect the probe and cap off both ends. 2) Disconnect

the line joining

the cyclone

oven to •he XAD-2 module at the exit side of the filter

and cap off a) the entrance

to the I0• •yclone,

b) the filter holder exit, and c) the entrance

to the join line which was disconnected

from the filter

holder

exit point. 3) Disconnect

the line joining

the XAD-2 module

to the impinger system

at the point where it exits the XAD-2 module. Cap off the exit of the XAD-2 module

and the entrance

line to the impinger

system. 4) Disconnect

the line exiting

the drierite

impinger

at the point where it leaves

the impinger

and cap off the impinger

exit.

Discard

ice and water from the impinger box to facilitate

carrying. The solvent

system

which has been found to be the most effective

for line rinse and final cleanout

of adhered

sample

consists

of a l:l mixture of methylene

chloride

(CH2CI2)

and methanol

(CH3OH). Since step-by-step

procedural

instruction

in narrative

.form would be voluminous, time-consuming

to follow,

and might be confusing

to the reader, each Step is presented

in the following

series

of flow diagrams

(Figure

12 to Figure

14). It is suggested

that these diagrams

be placed

in an easily visible lo'cation

near the cleaning

area as an aid to the sample

transfer activity. 3.6 OPACITY

MEASUREMENTS Opacity of stack effluent

gas is a required

Level 1 data point for each sampled

stack.

The method

to be used for this evaluation

is the iRingelmann technique

which involves

•he simple

process

of comparing

stack effluent opacity

to a hand-held

grid composed

of varying

shades

of grey from white to black.

The technique

usually

requires

a person

who has been certified to take the reading;

however,

for Level I purposes,

this require-. ment has been waived.

411

I

4243STEP

NO.

COMPLETE XAD.-2 MODULE AFTER SAMPLING RUN

RELEASE CLAMP JOINING XAD-2 CARTRIDGE SECTION TO THE UPPER GAS CONDITIONING

SECTION

REMOVE XAD-2 CARTRIDGE

FROM CARTRIDGE HOLDER. REMOVE FINE MESH SCREEN FROM TOP OFCARTRIDGE. EMPTY RESIN INTO WIDE MOUTH GLASS AMBER JAR

REPLACE SCREEN ON CARTRIDGE,

REINSERT CARTRIDGE

INTO MODULE. JOIN MODULE RACK TOGETHER. REPLACE CLAMP.

OPEN CONDENSATE

RESERVOIR VALVE AND DRAIN AQUEOUS CONDENSATE INTO A LITER SEPARATORY FUNNEL. EXTRACT WITH CH2CI 2 STEP NO. 2 CLOSE CONDENSATE

RESERVOIR VALVE

ELEASE UPPER CLAMP AND LIFT OUT INNER WELL

WITH GOTH UNITIZED WASH BOTTLE (CH2CI2:CH3OH) RINSE INNER WELL SURFACE INTO AND ALONGCONDENSER WALL SO THAT RINSE RUNS DOWN THROUGH THE MOOULE AND INTO CONDENSATE

COLLECTOR

PLACE TO ONE SIDE

RINSE ENTRANCE TUBE INTO MODULE INTERIOR. RINSE DOWN THECONDENFLOW DOWN THROUGH THE SYSTEM SER WALL AND ALLOW SOLVENT TO AND COLLECT IN CONDENSATE

CUP

RELEASE CENTRAL CLAMP AND SEPARATE THE LOWER SECTION (XAD-2 AND CONDENSATE

CUP) FROM THE UPPER SECTION(CONDENSER)

THE ENTIRE UPPER SECTION IS NOW CLEAN.

TION INTO THE CONDENSATE

CUP

RELEASE LOWER CLAMP AND REMOVE CARTRIDGE

SECTION FROM CONDENSATE

CUP

THE CONDENSATE

RESERVOIR NOW CONTAINS ALL RINSES FROM THE ENTIRE SYSTEM. DRAIN INTO AN AMBER BOTTLE VIA DRAIN VALVE.

Figure 13, Sample

Handling

and T•ansfer

XAD-2 Module

44ADD RINSE FROM CONNECTING LINE LEADING FROM XAD-2 MOD TO FIRST IMPINGER

DIST. H20 AND ADD

!MPINGER NO. 2

NALGENECONTAINER

DISTo H20 AND ADD •| MEASURE TOTAL J VOLUME FOR SINGLE ANALYSIS

DRIERITE DISCARD

Figure 14. Sample

Handling

and Transfer

Impihgers

453.7 DATA REDUCTION Due to the complexity

of the SASS train,

a broad range of data is acquired as the result

of each run. The subject

of data reduction

isdiscussed in detail

in ChBpter

I; however,

certain

aspects

specific

to SASS train samples

are briefly

presented

here. After the laboratory

analyses

have been

performed

for a specific

sample, the data can be applied

to the process

as a whole.

For example,

if the laboratory

analysis

detects

5 ppm Hg in a specific

sample,

this quantity

can be applied

to the weight

of the total sample

that was collected,

and can then be further

used to calculate

the mass emission

rate of the entire stream being characterized.

In general,

the process

parameters

andconditions determined

during

the pre-site

survey

(Section

3.3.1) will serve as the data base to which the analysis

results

can be applied.

For example, data on duct or stack stream

velocity

and grain-loading

density

is used to calculate

the particulate

concentration

and size distribution

within

a stream once the particulate

weights

from the cyclones

and filter

aremeasured. As a result

of the data reduction

process,

general

process

effluent profiles can be developed

for each parameter

of interest.

The molecular weight or class of organic

or inorganic

species

may be plotted

as afunction of its location

throughout

the train.

Volatility

factors

of particulate matter versus

gas may be developed.

Data points

resulting

from bioassay analyses may be accumulated. Data reduction

relationships

may also be drawn through

a comparison

of established matrices.

For example,

it may be noted upon comparison

that a relationship exists

between

the organic

matter

distribution

matrix

and the bioassay matrix.

Eventually,

after several

sampling

efforts

have beenconducted for a specific

process

type (e.g.,

power plants,

coal gasification operations, etc.),

a complete

characteristic

effluent

profile

for that specific process

may be established.

46CHAPTER IV FUGITIVE EMISSIONS

SAMPLING
4.1 INTRODUCTION

(References

2, 4, 27) Fugitive emissions

are those air and water pollutants

generated

by any activity

at an industrial

site which are transmitted

from their source directly into the ambient

ai• or receiving

surface

and ground

waters

mithout first passing

through

a stack,

duct, pipe or channel

designed

to direct
or control

their flow.

The assessment

of the effect

of a specific

fugitive emission on the environment

requires

determination

of the amount

ofpollutants entering

the atmosphere

or receiving

waters

on a weight-or-volume per-unit-time basis. This chapter

presents

the basic strategies

for the sampling

of air-and waterborne fugitive

emissions

in Level I assessment

effort.

The sampling programs are' designed

to provide

estimates

of the major process

components emitted as fugitive

emissions,

within

the accuracy

limits

discussed,

in Chapter I.Fugitive emissions

may be generated

by almost

any industrial

operation, including those with specific

emission

control

equipment.

Airborne

fugitive emissions consisting

of particulate

matter

and gaseous

pollutants

may be generated by sources

enclosed

in buildings

and transmitted

to the atmosphere

through structural openings

or vents,

or generated

by sources

in open areas and transmitted directly

into the atmosphere.

In this chapter,

any source within a given site generating

fugitive

emissions

which contribute

tooverall concentrations

will be called

a specific

source.

The overall

fugitive emissions concentration

resulting

from the sum total of specific

sources will be referred

to as the site source.

Waterborne

fugitive

emissions, which consist

primarily

of suspended

and dissolved

solids,

may be generated by process

leaks and spills,

runoff

from a wide variety

of material

storage piles, and fallout

from emissions

initially

airborne.

They are transmitted to surface

waters

by runoff

and to ground

waters

by infiltration.

Figure 15 summarizes

the sampling

categories

for Level l airborne

fugitive emissions.48Because of the unique

nature

of fugitive

emissions,

special

techniques applicable to their diffuse

nature

are used.

These techniques

include upwind-downwind sampling

techniques

for site sources,

downwind

and free plume techniques

for specific

sources,

sampling

for waterborne

fugitive emissions transported

to surface

waters,

and percolation

studies

forwaterborne fugitives

transported

to ground

waters.

The basic aim of this survey effort is not the precise

quantitifcation

of a given plant's

fugitive emissions, but the determination

of the fugitive

pollution

potential

so that
a detailed

Level 2 effort

can be planned

and executed

with a minimum

amount of wasted

effort. Unlike other chapters

in this manual,

the fugitive

emissions

chapter must be divided

into two distinct

parts in order to avoid confusion.

The first part considers

airborne

fugitive

emissions

while the second

considers fugitive emissions

as they relate

to waterborne

contaminants.

Thediscussions include

technique

descriptions,

equipment

r•quirements,

system design and data reduction

and manpower

requirement

estimates. 4.2 AIRBORNE

FUGITIVE

EMISSIONS 4.2.1 Preparation

for Sample

Collection

(References

27, 28,

29) The following

sections

discuss

the preliminary

procedures

required for sample

collection,

including

the pre-test

site survey,

the preparation of measurement

equipment,

and personnel

requirements. 4.2.1.I Pre-test

Site Survey The pre-test

site survey

for airborne

fugitive

emissions

is extremely site specific

and consequently

requires

many subjective

judgments

and is treated here in a very general

manner.

The predominant

portion

of the survey activity

will involve

a tour of the overall

site in an attempt

to identify existing

specific

sources.

If specific

sources

are found to exist, they must be placed

in one or the other of the following

two categories: l) A specific

source

which generates

a highly

diffuse cloud .over an extensive

area, such as coal or ash storage piles. 2) A specific

source

which generates

an emission

which might be broadly

or generally

classified

as a plume, such as a coke oven bank.Naturally, a wide variety

of specific

sources

fall into a nebulous

area which could apply to either

one of the above two definitions.

When this problem

exists,

the source

is to be assigned

to the first category.
In addition,

a specific

source under consideration

for fugitive emissions sampling

must be significant

enough

to warrant

the effort involved in making

the characterization. This is also subjective

and a pro or con'declsl•n

must hinge on the likelihood

of the emission's

migration beyond

the site boundaries.

If uncertainty

exists

concerning

specific

source significance

criteria,

disregard

the source

under the assumption •hat the site source

samples

will supply

the needed

data. Having identified

sampling

positions

for all significant

specific

sources within

a site, the next step involves

locating

suitable

upwinddownwind locations

for the site source

samplers.

One or more upwind

and downwind samplers

are required,

which depends

on the location,

size of the site or the homogeneity

of the emissions

as they exist at the boundary

areas. Clearly,

in view of the above criteria,

a specific

example

cannot

be developed to consider

the diverse

contingencies

likely

to be encountered throughout a variety

of sites.

However,

an understanding

of the magnitudes involved is facilitated

by considering

optimal

sampler

locations

for a "worst case" site.

Such a site is considered

in the decision

example shown in Figure

16 wherein

optimum

sampler

locations

are indicated

for various specific

sources

as well as For the overall

site,

This decision aid is discussed

in detail

in. Section

4.2.3. 4.2.1.2 Measurement

Equipment

(References

21, 27, 30) High Volume

Sampler.

The high volume

sampler

package

identified

for Level l sampling

consists

of three primary

components:
2)3) A commercially

available,

high volume filter

device for particulate

matter

identification, An XAD-2 absorbent

trap for >C 6 organics,

and; A 5-cfm pump for the

XAD-2cartridge.

50x

51In most common

types of high volume

filters,

a high speed vacuum-cleaner type motor is utilized

to draw large volumes

of air through

a filter

to trap the entrained

particulate

matter

on the filter

surface. A number

of such devices

are commercially

available

and may be utilized interchangeably if the following

general

specification

can be met:

• Flowrate

This should

be variable

between

O.57m3/min and 1.7m3/min

(20 to 60 cfm).This

variability

is needed in order to compensate

for differences

in particulate density.Filter size

20.3cm

x 25.4cm

(8"xi0")

Spectrograde glass fiber filters

(Gelman

Instrument

Co. or equivalent). Automatic Flow Control

Most commercial

instruments have optional

automatic

devices

to keep a constant flowrate as particulate

matter

builds

up. This type ofcontrol is recommended

to promote

accurate,

unattended flow control.

• Construction

Lightweight

and durable,

capable

ofallweather operation

in plant environments. Cyclic Timer

The sampler

should

have the capability to sample

continuously

for a set period

of time or intermittently during a sampling

period

to match the cyclic nature

of plant processes.

• Electric

Generator

In many cases,

a portable

electric generator(s) will be required

to operate

the samplers.
In addition

to these requirements,

it is recommended

that a particulate size fractioning

head be added to the high volume

sampler.

Particle

size fractioning heads are available

(Anderson

2000 Inc.) which fit directly

on high volume

samplers.

For Level 1 sampling,

a single

stage head (40 cfm) providing a cutoff

at 3.5u and

a back-up

filter

is recommended. Grab sampling

of gases may be accomplished

using 3-1iter

containers

as described

in Section

2.3.3, The XAD-2 adsorbent

trap is described

as part of the source

assessment sampling system

(SASS) train in Chapter

Ill. A similar

trap (eqpal

in volume but with different

end fittings)

is connected

as an integral

part of this system

as indicated

in Figure

17.

52I/4

INCHSWAGELOK BULKHEAD

COPPERTUBING WALL/

CONNECTOR "• "

TO 5 cfm PUMP Figure 17. Expanded

View of Connections

of XAD-2 Cartridge to High Volume

Sampler

53SASS Train.

A detailed

description

of the SASS train which is to be used to sample

Category

2 specific

sources

which generate

plumes

is presented in Chapter

Ill. A detailed

discussion

of the application

of the SASS train to fugitive

emissions

sampling

will be presented

below in Section

4.3. 4.2.1.3 Personnel

Requirements

(References

l, 2, 27, 29, 31) As an outgrowth

of the pre-test

site survey,

the exact number

of sampling locations

required

for the fugitive

emissions

study may be used as the basis for establishing

manpower

projections.

Two team members

are required to set up each high volume

sampling

station.

Assembly

andactivation will require

approximately

two hours depending

on sampling

site accessability. Standard

sampler

housings

as specified

in Federal

Register, Part 50, Section

5 (Ref. 30) are sufficient

for Level l purposes;

long elevating poles or platforms

are not required.

After activation,

sampler operation is automatic

and does not require

supervision.

Manpower

requirements for the hi-vol

sampling

matrix

may then be estimated

as a function of the anticipated

number

of sampler

locations. As indicated

in Chapter

Ill, Section

3.3.2,

the SASS train requires

two and in some cases three persons

for assembly

and disassembly.

One to one and one-half

persons

are required

for operation.

These projections

apply only to stack or duct sampling

conditions

where railings,

platforms

and supportive port openings

are available,

however.

For fugitive

emissions sampling, few or none of these conveniences

will exist.

The probe will in many cases have to be held or at least supported,•manually; continuous supervision will be required

to ensure

that the probe is held within

the emissions plume.

Obtaining

the required

amount

of Sample

(see Tab1•e •1) will often require

extended

sampling

periods.

Often,

site geometry

will require remote

equipment

setup with lengthy

webbed

cable probe extensions. which in turn will require

heat tracing.

These and a variety

of other factors must be considered

(depending

on specific

site requirements)

before manpower estimates

for this activity

can be established. A best possible

case assembly

and disassembly

will require

from 3 to 4 persons; operation

will require

no less than two persons.

Still,

a best possible

case setup will require

from 5 to 6 hours and the operating

54pe•tod w111 depend

on the density

of the plume and the frequency

of the cyc]e.(assumlng the process

is cyclic).

The decision

to place a specific
source in Category

2 for cost effectiveness

reasons

must not be made lightly. Figure

16 can again be used to clarify

the genera]

process magnitudes applicable

to specific

sampling

types. 4.2.2 Sampling

Procedures

(References

27, 28, 29,

30, 31) 4.2.2.1 Htgh Volume

Sampler

Applications The modified

high volume

sampler,

as described

in Section

4,2.1.2,

will be used in all ftrst category

specific

sources

(see Section

4o2.1.1)

and all site source

sampling

operations. The number

and location

of upwind-downwind

devices

used to collect samples are extremely

important

to the sucdessful

completion

of a Leve] 1 sampllng matrix.

The design

of the system

is influenced

by such factors
as source

compiexity

and slz•, site geometry

and prevai]ing

meteorological conditions. Generally,

only one upwind

device

is required

in order to supply background

data and one or more downwind

samplers

are needed

depending on the above stated

factors.

Downwind

site-source

samplers

are to be removed as fa• as possible

from any process

operatioq

since the objective tn this case tnvolves

the collection

of a measured

portion

of a homogeneous cloud as it passes

beyond

the plant boundary. First category

specific

source

samp]es

need only be taken on thedownwind side of the source.

These samp]es

a•e all taken external

to the source and should

be placed

within

the actual

cloud if possible.i

In contrast

to the site source

samplers

which are removed

as far as possible

from any process operaton,

specific

source

samplers

are placed

as close as possible tO the actual

speclftc

source. Subjective estimates

of existing

cloud densities

may be •plted

to the curves provided

in Figure

18 as a general

guideline

for time versus

flowrate settings.130

120

0100

RO

2O (60 CFM) ow •

0

.566 M3/MIN FLOW (20 CFM)

FLOW RATE CURVE TO BE USED WHEN DUST CONCENTRATIONS

ARE ARE NOT VISIBLE

CLEAR l• VERY LIGHT HAZE 0

iO0 200 300 ,•G PARTICULATE/M

3 IN AMBIENT AIR

FLOW RATE CURVE TO BE USED UNDER HAZE CONDITIONS

LIGHT HAZE

II, HEAVY HAZE R00

300 400

500 700 900 II00

FLOW RATE CURVE TO BE USED WHEN DUST CONCENTRATIONS ARE VISIBLE

HEAVY HAZE

•' THICK DUST

Figure 18. Sampler

Flow Rate Settings

for Dust4.2.2.2 SASS Train Sampler

Appllcations Fugitive emissions

falling

into the second

specific

source

category (see Section

4.2•I.1)

are sampled

with the SASS train.

The minimum

sample quantities per run, as shown in Table l, apply here as well. No two second

category

specific

sources

will ever have the same (or

even similar)

site geometry.

Plume characteristics

(temperature,

area, ve10clty, density,

composition,

cyclic

frequency•

etc.) will also vary markedly depending

on process

type, size, meteorological

conditions

and the existence

or nonexistence

of control

devices.

Because

of these extremely diverse

conditons,

only generalized

procedures

may be presented concerning fugitive

emissions

characterization with the SASS train. The first consideration

involves

taking

every precaution

to ensure

the health and safety

of personnel

directly

involved

in the sampling

task. Personnel assembling

the train and especially

the person

responsible

for holding the probe in the plume will be either

partially

or totally

immersed .in the escaping

gases,

and depending

on the nature

of the effluent

varying degrees of protective

clothing

will be required.

Depending

on the length, of exposure

this may require

clothing

ranging

from a simple

dust mask to a complete fireproof

outfit

equipped

with self-contained

breathing

apparatus. The second

consideration

involves

.a choice

of the optimum

position

for sample.withdrawal. This position

cannot

be chosen

during

the survey

effort because specific

sources

of the second

category

(and in many cases,

in the first category

also) are dependent

on a number

of process

and meteorological variables which either

may or may not exist on the return

trip.

The optimum posi'tion for sample

withdrawal

should

also be an acceptable

location

for all train components

following

the .probe.

If the above integrated

arrangement is not possible,

the next best choice

involves

keeping

probe and cyclone Oven together

while removing

the rest of the components

towhatever

distance the process

geometry

demands.

If the arrangement

is such that room for the probe only exists,

the entire

rema•nder

of the system

must be placed

in aremote location.

In any case, where one component

of the train must be isolated from another

component,

the lines joining

the two must be heat-traced to avoid condensation.

Assembly

and operation

of the SASS .train is detailed in Chapter

III. A fugitive

emissions

sample

is taken with the SASS train by inserting the nozzle

into the plume or cloud and pulling

at the maximum allowable flowrate

using the largest

available

nozzl'e.

Naturally,

the closer the nozzle

to the emissions

exit point,

the denser

the plume and the shorter the sample

duration. 4.2.2.3 Gas Samples The acquisition

of gas samples

for fugitive

emissions

requires

very little elaboration

here.

All gas samples

for Categories

1 and 2, as well
as for site source

upwind-downwind, will be taken by the evacuated

grab sampling technique

which is presented

in detail

in Chapter

II. 4.2.3 Decision

Aid for Appropriate

Category

Selections As previously

stated,

the sampling

matrix

for airborne

fugitive

emission characterizatlon results

from the Choice

of three available

options:

site
source samples,

Category

l specific

source

samples,

and Category

2 specific
source samples.

The location

of sampling

positions

for the site source case simply

involves

selecting

the proper

sites for the

upwind

and downwind samples. Sampling

position

for specific

sources,

which must be classified into Categories

l or 2, are not as easily

identified

as the site source. For this reason,

a worst-case

model is presented

(Figure

16) in which a wide variety

of specific

sources

are known to exist.

The model,

which represents an integrated

steel plant is not intended

to be viewed

as a specific case representation,

but provides

an example

of many of the specific sources

found individually

in smaller

and less complex

operations grouped together

as an integrated

unit. As indicated

in Figure

16, Category

1 is assigned

to positions

in relatively open areas but which are near specific

sources

of emissions: downwind from coal and coke piles,

and limestone

bins; and downwind

from blast furnace

and sintering

operations,

ore-treating

operations,

coke quenching and grinding

operations.

Category

2 is assigned

to positions where plumes

are generated,

such as •oke •ve•.ba•k,and

an open hearth furnace.4.2.4

Sample

Handling

and Shipment

(References

3, 4, 6, 25) Quantitative transfer

of the samples

from the 3,5• size fractionating head and the filter

is necessary

in order to determine

existing

partlculate densities. The > 3.5• catch can be removed

from the head by tapping

the head and carefully

brushing

any adhering

material

i•to a tared high density N•Ige•e

shipping

container.

The glass fiber filter

must be transferred into a petri,dlsh

and sealed

without

particulate

matter

loss. During the sampllng

process,

the filter

materlals

have been subjected

to conditions which tend to weaken

their cohesive

properties,

so care must be taken to prevent

filter

fragmentation

during

the transfer. After the sample

containers

have been sealed,

the samples

may be taken to the mobile

van for shipment

to the laboratory. The XAD-2 cartridges

are emptied

into amber glass jars with Teflon

seals and shipped

to the laboratory

for extraction

and analysis.

The exact procedures for SASS train sample

handling

and train clean-up

are given in Chapter III.SASS Train Samples

Lines and containers

are rinsed

with methanol/ methylene chloride

and stored

in an amber bottle. Gaseous Samples

All gass bulb samples

are taken to the mobile

facility for on-site

instrumental

analysis. 4.2.5 Data Reduction

for Airborne

Fugitive

Emissions

(iReference

2,
When the sampling

program

has been completed

and the samples

have been analyzed to yield qualitative

pollutant

concentrations

in such terms as micrograms per cubic meter in the ambient

air at the individual

or combined downwind sampling

sites,

the measured

upwind

concentrations

are subtracted to yield the concentration

provided

by the source

at each sampler.

A library of computer

programs

to assist

in the performance

of this assessment is maintained

in the User's

Network

for Applied

Models

of Air Pollution (UNAMAP) atthe

Environmental

Protection

Agency's

Research

Triangle

Computer Center. Additional

programs

may be obtained

through

many environmental consultants.

594.3

WATERBORNE

FUGITIVE

EMISSIONS 4.3.1 Preparation

for Sample

Collection The following

sections

discuss

the preliminary

procedures

required

for sample collection,

including

the pre-test

site survey,

the measurement techniques required,

and personnel

requirements. 4.3.1.1 Pre-Test

Site Survey

(References

32, 33, 34, 35, 36) Like airborne

fugitive

emissions,

waterborne

fugitive

emissions

are very site specific.

In designing

a water fugitive

emissions

survey,

the following general

strategy

should

be used: I) Assess

operating

procedures

to see where waterborne

fugitive emissions originate,

e.g., material

storage

piles,

overflow from impoundments,

runoff

from construction,

dust from conveyors. 2) Obtain

the necessary

background

information,

including

topographic data, soil data, geological

information,

hydrology, climatology and meteorology,

surface

cover,

land use. 3) Locate

runoff

sampling

stations

based on the drainage

basins identified from a topographic

survey. 4.3.1.2 Measurement

Techniques

(References

32, 33, 34, 35, 37) A variety

of techniques

for the measurement

of waterborne

fugitive emissions is in use today.

These techniques

include

water runoff,

receiving body sampling

and core sampling.

The method

of choice

for the Level I characterization of waterborne

fugitive

emissions

is surface

runoff sampling.This method

is utilized

for sources

that can be identified

ascontributors to the pollution

of water at an industrial

site and whose runoff

during a rainfall

may be isolated

from that of other sources.

An example

of such a source

is a storage

pile containing

materials

which will be carried either as suspended

or dissolved

pollutants

by surface

runoff

to the environment outside

plant boundaries. Topographic data and a site survey

are used to locate

an array of samplers arranged

to collect

representative

portions

of the runoff

during

a rainfall.

The samples

are usually

located

in the ground

as close to the
source as possible

and in natural

gullies

and channels.

Samples

are taken
60at

the onset of a rainfall

and at intervals

during

the rainfall

and analyzed to determine

the. change

in pollutant

concentration

as a function

of the amount of runoff

determined

by rain gage measurements.

This change

inconcentration may be used to estimate

the amount

of polluting

material

that may be expected

to reach the receiving

body as a result

of any single

or an entire season's

rainfall. 4.3.1.3 Personnel

Requirements Personnel requirements

for placing

the sampling

plugs are in most cases minimal. One team member

will be able to complete

the activity

in arelatively short period

of time.

The actual

time required

is dependent

on the proposed area of the monitored

zone and the ease of accessibility

to that

area.4.3.2 Sampling

Procedures

(References

38, 39, 40, 41)
For the sampling

of contaminated

runoff,

such as a material

storage pile, plug collectors

similar

to that shown in Figure

19 are used.*

The plugs are driven

into the ground

at selected

locations

where runoff

will occur, such as at the base of the material

pile, and in material.gullies and channels.During

a rainstorm

or snow-melt,

the collectors

are changed

atappropriate intervals

depending

upon runoff

intensity.

The collector

contents

are measured

and analyzed

for pollutants

as discussed

in Chapters

VII and VIII. An estimate

of the runoff

flow is made from

total rainfall

data and soil permeability

in the test area. 4.3.3 Decision

Aid The area designated

for characterization must be carefu11y

studied

by those individuals

responsible

for this activity.

Key areas to identify

are:

e Coal piles

• Waste piles

• Drainage

trenches

for plant system

runoff,

and

• Possible

overflow

areas from holding

ponds. Plugs are designed

and built by Kahl Scientific

Instrument

Corp., P.O. Box 1166, El Cajon,

California

92022
61SURFACE WATER
•,• ••••]

ENTRANCE

GROUND WATER SEEPAGE

Figure 19. Plug Collector

for Fugitive

Water Samples
Good areas for collector

placement

are:

• Areas of lowest

elevation

where sample

throughflow

is evident,

• Drainage

ditches

or channels,

and Any areas between

the complex

under consideration,

and a receiving body of water. Maximum precaution

must be taken to ensure

proper

collector

placement

so that data obtained

may be related

to the proper

source.

Water runoff

samples are similar

to airborne

fugitive

emissions

in that both specific
source and site source

samples

are obtainable.

Collectors

placed

for general plant runoff

are analagous

to site source

upwind/downwind

samples, and collectors

placed

for specific

problem

areas are analagous

to specific
source downwind

Samples.4.3.4

Sample

Handling

and Shipment Runoff samples

from specific

sources

are to be combined

in order to perform a single

analysis

to characterize

a potential

problem

area.

This minimizes the error which might otherwise

result

from sample

analysis

on a unit basis.After combining

the samples

obtained

from a specific

source

together into one unit, the resulting

single

sample

is subjected

to the sameseparation scheme

indicated

in Figure

23 (Chapter

V). The only digressions from the Figure

23 flow plan are: I) BOD and COD analysis

are not performed,

and 2) A lO-liter

volume

is not required. The stabilization

procedure

applicable

to the resulting

phases

must concur with the directives

indicated

in Table 3. 4.3.5 Data Reduction

for Waterborne

Fugitive

Emissions

(References

33, 37, 39, 41)The samples

obtained

from the runoff

plug samplers

are analyzed

to provide pollutant

concentrations

as a function

of time from the start of the sampling

period

rainfall.

Plotted

against

the measured

rainfall

rate, they will provide

an estimate

of the amount

of pollutant

that can be expected to be received

for that period,

and, by extrapolation,

the amount of pollutant

that can reach the receiving

body for any given number

ofrainfalls. Historical

meteorological

data on the average

or maximum

rainfall frequency and rate can then provide

an assessment

of the site or source contribution for a seasonal

period. Figure 20 is a block diagram

summary

of the waterborne

fugitive emissions Level I assessment

programs

described

in this section.WATERBORNE FUGITIVE EMISSIONS

SOURCES

SURFACE RAINWATER RUNOFF

PLUGSAMPLERS

SAMPLE J
ANALYSES RAINFALL MEASUREMENT

HISTORICALDATA

DATAREDUCTION

Figure 20. Level 1 Water Runoff

Fugitive Emissions Characterization

64CHAPTER V LIQUID AND SLURRY

SAMPLING
5.1 INTRODUCTION In any given industrial

process

operation,

the probability

is high that

a number

of the influent

and/or

effluent

streams

will exist in liquid

or slurry form.

Considering

the multiplicity

of liquid

or slurry

streams

in typical plants,

the number

of possible

sampling

points

becomes

extensive. Figure 21 summarizes

the types of streams

generally

found in industrial operations and the sampling

•thods

to be used.

It should

be noted that these streams

are transported

in a variety

of ways which may range from closed pipes to open ditches

and sluices.

The three methods

chosen

for the Level I sampling

of liquids

and slurries

are heat exchange,

tapsampling and dipper

sampling.

Each method

is discussed

in detail

in Section

5.3. Once the samples

are collected,

they may be analyzed

on site or packaged for shipment

and analysis

at the laboratory

(see Chapters

Vll and

PROCESS STREAMS

LIQUIDS CONTAINING

MISCIBLE AND IMMISCIBLE

PORTIONS, WITHOUT SOLIDSB,C ;UPERHEATED

LINES

A

MOLTEN SOLID LINES

SLURRIES

B,C

SAMPLING METHODS A HEAT EXCHANGE B TAP SAMPLE C DIPPER SAMPLE
*TAP SAMPLE MAY BE TAKEN IN LINES OF THIS NATURE ONLY IF THE/vVkTERIAL

IS LIQUID AT RELATIVELY

LOW TEMPERATURES

(i .e., CERTAIN PETROLEUM

TYPES)
Figure 21. Sampling

Methods

as a Function of Stream

Type.65VIII). Streams

may be organic

or aqueous

or may contain

water/organics/ solids in miscible

or immiscible

fractions.

The handling

of these solutions will affect

the reliability

of the chemical

or biological

tests performed. Section 5.4 proposes

a tentative

field separation

scheme

to prevent

sample loss or adulteration.

This scheme

is comprehensive

enough

to prevent sample los•, but is simple

enough

to implement

in the field. 5.2 PREPARING

FOR SAMPLE

COLLECTION 5.2.1 Pre-Test

Site Survey The same criteria

for locating

a gas sampling

point can be applied

to locating sampling

sites for liquid

samples.

A review

of those criteria and procedures

is contained

in Section

2.2, Chapter

II. While the site selection

criteria

for gas and liquid

sampling

are generally the same, the test personnel

must be aware of the problems associated with the sampling

of liquids

and how these factors

affect

the choice of a sampling

site.

Two factors

will affect

the selection

of a sampling site for liquid/slurry

streams:

• Stream

Homogeneity

This is the most important

problem that must be addressed

by the site survey

crew.

Unlike gas streams

which mix fairly

evenly,

liquid

streams

tend to be more stratified

because

of lower thermal

agitation and higher

fluid viscosities.

• Stream

Flowrate

Large,

slow-moving

streams

will offer more of a chance

for stratification

to occur.

This factor is especially

important

in large pipes or open. sluices and ditches. These factors

indicate

that free-flowing

streams

should

be sampled after points

of turbulence

(elbows)

to collect

samples

of maximum

homogeneity. Because

of the possible

stratification

in slow moving

open streams, a sampling

point should

be chosen

so that a full stream

cut can be made with a dipper

sampler.

Sluice

gates or pipe outfalls

offer a good opportunity to obtain

a sample

in this fashion. In all cases the main pipe or stream

flow should

be sampled.

Because solids can accumulate

in seldom-used

vent or slip streams,

these lines are not recommended

for sample

acquisition.

Long slip stream

lines are to be avoided, but can be used if the main line is inaccessible

and if the slipstream line is f•us••wi•h

several

times 'the volume

of liquid

held in the line between

the main line and the tap. 5.2.2 Personnel

Requirements The liquid

and slurry

sampling

techniques

presented

in this chapter

are uncomplicated,

and under favorable

conditions

only one person

is needed to perform

the sampling

effort.

The•e are conditions,

however,

whereadditional manpower

will be required.

Many streams

will require

that a crew member work under conditions

or in areas where the potential

for physical mishaps is high.

For example,

using a dipper

to sample

an open stream might require

a crew member

to extend

himself

physically

to reach the sampling point either

by leaning

from catwalks,

reaching

from ditch banks,

or physically

wading

in the stream.

In other cases,

the closed

stream

will be under high pressure

and temperature

which will multiply

the dangers involved in taking

a sample.

An additional

crew member

should

be present here to ensure

the safe completion

of the task even though

his active presence is not necessary

for the sampling

effort. 5.2.3 Equipment

Preparation 5.2.3.1 Sample

Containers Containers intended

for sampling

industrial

water streams

must be made of a high density

polyethylene

or polypropylene.

Plastic

bottles

for aqueous stream samples

should

be cleaned

by: a) Detergent

wash, followed

by b) Distilled

water rinse,

followed

by c) 1:1 sulfuric

and nitric

acid mix. Organic samples.,

including

CH2CI 2 extractions,

must be placed

in amber glass bottles

to inhibit

sample

degradation.

These amber

glass bottles area)b)c)d)e)f) cleaned

by: Strong soap solution, Liberal tap water rinse, Distilled water rinse, Methanol rinse, Methylene chloride

rinse,

and Drying a clean,

hot air stream

or by placing

in an oven at 40oc (140°F).After the apparatus

has been cleaned

and d•ied,

it should

be stored in boxes to prevent

spurious

contamination. 5.2.3.2 Apparatus Sampling lines should

be as short as possible

to facilitate

flushing and to reduce

time lag. The lines must have sufficient

strength

to prevent structural failures.

Lines intended

for sampling

streams

under pressure must be designed

in accordance

with the specifications

outlined

in the American Standard

Code for Pressure

Piping.

Where small diameter

capillary tubing is used, it should

be protected

by a sheath

of larger

diameter

pipe of adequate

structural

strength.

Materials

of construction

should

conform to the applicable

specifications

of the American

Society

for Testing

and Materials as follows:Pipe (seamless

ferritic

alloy-steel

for high temperature service) ASTM Designation

A335. Tubing (seamless

carbon-steel

for high temperature

service) ASTM Designation

A179.

• Tubing

(seamless

alloy-steel

for high temperature

service) ASTM Designation

A608. Valves and fittings

must be fabricated

from materials

similar

to those used in the sampling

lines and must also conform

to the requirements

of the specifications

of the American

Society

for Testing

and Materials

as follows:

• Steel (suitable

for fusion

welding

up to 850°F)

ASTM Designation A216

• Steel (carbon

forged)

ASTM Designation

Al05

• Steel (alloy

steel castings

for use up to llO0°F)

ASTM Designation A217. Materials for fabrication

of sampling

apparatus

not intended

for use in pressure

applications

are not required

to meet such stringent

specifications due to the significantly

reduced

safety

requirements.

The primary

element of importance

here is the fabrication

of equipment

from materials

which will not contaminate

the sample.

It is preferable,

therefore,

that the sampling lines and collection

reservoirs

used for sampling

liquid

streams

be made of Teflon because

of its superior

chemical

inertness

toward

strong

acids, alkalis, and other chemical

reagents.

68All portions

of the sampling

apparatus

which come into contact

with the sampled

stream

should

be cleaned

using the same procedure

that was used in cleaning

the container

for that sample

(see Section

5.2.3.1). 5.3 SAMPLING

PROCEDURES

(References

42, 43)
As indicated

in Figure

21, all liquid

and slurry

streams

can be divided into distinct

sub-groups,

each defined

as a function

of the physical

makeup of the stream.

Each stream,

having

been so identified,

may be assigned

a sampling procedure

applicable

to that stream

type.

As indicated

inFigure 21, three specific

methods

are applicable;

they are: a) Heat exchange, b) Tap sa•ling,

and c) Dipper

sampling. Where the stream

to be sampled

exists

at a pressure

high enough

above atmospheric to provide

an adequate

sample

flow rate, the removal

of the •ample presents

no problem.

At near atmospheric

pressures,

special means must be provided

to establish

sample

flow.

This problem

can beovercome by u•ing either

a small pump to deliver

the sample

to the sample

container organ evacuated

sampling

vessel.

Prior to sample

acquisition,

all

new sampling

lines should

be purged

with line fluidto

remove

any deposits in the system

lines and to condition

the sampling

lines.

The period

of time required will depend

on the system

line size and distance

from the main stream. Once the lines have been flushed,

sampling

can begin.

A lO-liter sa•le is required

to perform

the analyses

identified

in Chapters

Vll.. and VIII.5.3.1 Heat Exchange

Sampling

Systems

for High Temperature

Lines
The majority

of .industrial

systems

utilize

steam for a variety

•f process applications

ranging

from relatively

clean power plant operations to polluted

lines resulting

from stripping

operations

involving

acid units, catalyst regeneration

and scrubbing

of polluted

gas streams.

In addition to pressurized

process

lines,

various

other process

operations

exist which contain superheated

vapors

Composed

of effluents

generally

characterizableas

reaction

products.

The sampling

techniques

described

in this section pertain to all of •he above systems;

however,for

the sake of brevity,

the term HT line (high temperature)

will be used to represent

all applications, unless otherwise

indicated. The principle

used in the sampling

of HT lines involves

the use of a water-cooled condenser

system.

Typical

examples

of apparatus

used for this purpose are illustrated

in Figure

22. As can be seen in Figure

22, two approaches are possible

depending

on whether

the pressure

in the line is above or below atmospheric

pressure.

The condensate

from the stream

is collected in a reservoir

for later analysis. In sampling

HT lines,

it should

be kept in mind that stream

constituents will to some degree

dissolve

any substance

contacted.

For this reason, the area of the surfaces

exposed

to the sample

and the time that the sample is in contact

with these surfaces

should

be kept to a minimum. As indicated

earlier

in paragraph

5.2.3.2,

all.tubing,

valves,

nozzles, and containers

must be constructed

from materials

of sufficient

strength

to withstand the full pressure

of the stream

being sampled.

Tubing

diameter must be small enough

so that storage

within.coils

and tubing

and the resultant time lag of the sample

through

the system

are minimal.

Thesampling operations

presented

in this section

may be used with complete

safety provided that proper

caution

is exercised. 5.3.2 Tap Sampling

(Reference

44) Contained liquids

may be divided

into two broad categories:

those which are in motion

(lines)

and those which are not (tanks or drums). Usually, a specific

sampling

technique

is applied

to each of the above two categories

in order to accommodate

the differences

in sample

characteristics, such as stratification. A flowing

stream

containing

particulate mattem will be stratified.

A tank sample

may also be stratified

but in the static

sense rather

than in the fluid sense.

Moving

streams•are

traditionally sampled

using a techni, que called

continuous

sampling.

This involves sample removal

from a tap which is connected

to a probe inserted

into the line, Static

liquid

samples

(tanks or large drums)

are sampled

using a techDique called

tap sampling.For the purposes

of Level 1, the effort

of inserting

a probe into the line is too time-consuming

to be efficient.

Consequently,

all contained liquids will be sampled

using the tap method,

as per ASTM D-270 (Ref. 44). Tap sampling,

as described

in this chapter,

describes

a wide variety of grab techniques.

In general,

this type of sampling

implies

that a sample is taken at a tap from a line or tank wall.

This approach

is used for moving

liquid

or slurry

streams.

The procedure

is also applicable

to streams under pressure

or elevated

temperature

provided

that the proper safety precautions

are exercised.

For systems

under pressure,

lines should be cracked

very slowly

to avoid injury

caused

by sudden

surge due to .entrained air pockets

or accumulated

solids

around

the valve opening. Streams under elevated

temperatures

should

be sampled

using a heat exchanger system

such as is described

in ASTM D-270 (Ref. 44). Tap samples

are collected

by inserting

the sample

line (a thOmoughly washed Teflon

line) into the sampling

bottle

so that it touches

the bottom. (After first flushing

the sample

line at a rate high enough

to remove

all sediment and gas pockets.)

The sample

bottle

should

be thoroughly

rinsed with sample

prior to filling

and the sample

line flow must be regulated

so
as not to exceed

500 ml/min.

If sampling

valves

or stopcocks

are not available, samples

may be taken from water-level

or gage-glass

drain lines
or petcocks. 5.3.3 Dipper

Samplin

9 The dipper

sampling

procedure

is applicable

to sampling

sluices

or open discharge

streams

of thick slurry

or stratified

composition.

The dipper is made with a flared

bowl and attached

handle,

long enough

to reach the sluice

or discharge

areas.

The bowl portion

must be coated with. Teflon.
A dipper

sample

is obtained

by inserting

the dipper

into thefreeflowing stream

so that a portion

is collected

from the full cross-section of the stream.

Sample

portions

are to be taken at time intervals

chosen
so that a complete

sample

is collected

which is proportional

to the pumped quantity. The gross amount

of sample

collected

should

be approximately 0.1 percent,

but not more than 40 gallons,

of the total quantity

being sampled. As noted previously,

this should

be at least 10 liters

or reduced to that quantity

for analysis.

72Although it is generally

agreed

that time-integrated

sampling

techniques are too sophisticated

for Level 1 application,

the lack in uniformity often found in thick or stratified

slurries

may require

special

consideration in some cases.

The site survey

will produce

information

on process cycles so that the sampling

times and points

cover the most representative period and location

of discharge. 5.4 LIQUID

SAMPLE

HANDLING

AND SHIPMENT As mentioned

previously

in Section

5.1, sample

handling

is an important consideration where liquids

are involved.

The entire

spectrum

of liquid samples exists

within

the bound•

of the following

six categories: 1) Aqueous2) Aqueous/organic 3) Organic4) Aqueous/solid 5) Organic/solid 6) Aqueous/organic/solid. These samples

must be stabilized

prior to shipment

for laboratory

analysis. Figure 23 shows a field handli:ng

scheme

for liquid/slurry

samples.

This scheme has been modified

(Ref. 45) to handle

suspended

particulate

matter. Figure 23 shows the worst ca•e (Aqueous/Organic/Solid), but is alsoapplicable to the simpler

cases. It is recommended

that in-field

separations

and specific

preservation techniques, rather

than a general

all-purpose

approach

that is not specific forinorganic, organic

and biological

prese[vation,

be followed.

Table 3 outlines the application

of Figure

23 to less complicated

systems.

It should be noted that both BOD and COD samples

are typically

taken before filtration. Sulfite

should

be determined

in the field and as soon as the samples are returned

to the lab.DRY AND WEIGH FOR TOTAL SUSPENDED SOLIDS

AQUEOUS/ORGANIC/SOLID 10 LITER SAMPLE• LITER TRANSFER[CAREFULLY
TO AVOID ENTRAINMENT-BOD, COD

FOR

SEE TABLE 3 FOR SAJ•APLE PRESERVATION AND CHAPTER VII FORINORGANIC MATERIAL ANALYSIS SEE CHAPTER Y[lJ FORORGANICANALYS1S

F•gure 23. Field Handling

Scheme

for Liquid/Slurry

Samples

7475CHAPTER VI SOLID SAMPLING
6.1 INTRODUCTION

(References

46, 47) Solid sampling

covers

a broad spectrum

of material

sizes from large lumps to fine powders

and dusts.

There is an equally

diverse

assortment of potential

sample

sites including

railroad

cars, barges,

trucks,

large heaps, plant hoppers

and conveyor

belts.

Obviously,

no one sampling

method

or piece of equipment

can accommodate

all possible

situations.

Furthermore, all of the above sampling

locations

may contain

products

of widely varying consistency.

For the purposes

of this chapter,

the consistency

of solid samples

ranges

by definition

from anhydrous

or dry solids

to thick, nonflowing pastes, The recommended

Level 1 sampling

technique

is the grab sample.

In general, the Level I and Level 2 solid sampling

techniques

are identical except that in the case of Level 2 sampling,

a series

of grab samples

is taken over a period

of time from a conveyor

belt or over a larger

area for stationary storage

sites such as railroad

cars or large heaps.

In cases of extreme

sample

variability,

a larger

grab sample

consisting

of several increments or shovelfuls

is required

on Level I, In most cases,

thedifference between

the Level l .sample

and a time-averaged

Level 2 sample

is only a matter of degree

rather

than of technique. The following

sections

present

the sampling

approaches

applicable

to input and output

solid streams

and storage

piles. 6.2 PRE-TEST

SITE SURVEY

(References

8, 48) Solid input and output

streams

in most process

operations

consist

of fuels, primary

reaction

components,

treatment

or maintenance

chemicals, salable output

products

or output

refuse

products.

These solids

range from very fine powders

to very coarse

lumps.

This variation

in sample consistency influences

the sampling

technique

to be used which must be establ%hed in thepre-site

survey.

For the purpose

of the pre-test

site survey, therefore,

the following

questions

must be answered: 1) Can the material

be sampled

as it enters

or leaves

the process, or must it be sampled

in its storage

or pile form? 762) If the material

can be sampled

as it enters

or leaves the process,

what is the nature

of the conveyor

system (belt, worm screw,

duct) and what is closest available sampling

location

to process

entry,

and farthest available

sampling

location

from process exit?3) What is the consistency

of the material

(powder,

coarse grain, lump) and what is the apparent

variance

within this consistency,

and 4) What is the approximate

size of the storage

reserve

and what is the method

of access

to said reserve? Each of these parameters

must be identified

before

the procedures

in the following

section

can be adequately

implemented. 6.3 SOLIDS

SAMPLING

PROCEDURES Level I solid sampling

procedures

use three manual

grab sampling techniques: shovel

or grab sampling;

boring

techniques,

which include pipe or thief sampling;

and auger sampling.

Data obtained

from thepretest site survey

concerning

the physical

characteristics

of the sample, together with the optimum

choice

of sampling

location

will determine

the appropriate sampling

technique.

Table 4 presents

a sampling

matrix

showing the appropriate

sampling

technique

as a function

of physical

characteristics and actual

location

of the sampling

points. Each of the grab sampling

techniques

is discussed

in detail

in the sections to follow. 6.3.1 Shovel

Grab Samplin•

IReferences

20, •2, 47, 49) Raw material

piles of relatively

coarse

lump size (ore piles,

aggregate piles, coal feed, etc.) are sampled

using a fractional

shoveling

technique. The shovel

Used in this procedure

is of the square-edged

variety

measuring 12.inches wide. In sampling

from belt conveyors,

one full cross-section

the width of the shovel

blade is taken as the sample. Where ladder

or tray conveyors

are sampled,

one shovelful

from one compartment is removed.Table 4. Decision

Matrix

for Solid Sampling

PHYSICAL NATURE OF SAMPLE FINE POWDER

COARSE POWDER

BE LTCONVEYORSN/A

N/A LADDER TRAY CONVEYOR SHOVELGRAB FROM ONE TRAY

SHOVELGRAB FROM ONE TRAY

SCREW

DUCT

OPEN

STORAGE BINS CONVEYOR SAMPLE

PILES

OR SILOS ONE SHOVEL

ONE SHOVEL PIPE OR PIPE OR FROM POINT FROM EXIT THIEF

THIEF OF EXIT

IF ENCLOSED FROM TOP IF OPEN ONE SHOVEL

PIPE

PIPE• THIEF.OR FROM POINT

THIEF OR AUGER OF EXIT AUGER ONE SHOVEL FROM EXIT IF ENCLOSED, FROM TOp IFOPE•N COARSE GRAIN

LUMP

CROSSSTEAM CUT, ONESHOVEL

CROSSSTE •J•4 CUT, ONESHOVEL SHOVELGRAB FROM ONE TRAY

N/A

ONE SHOVEL FROM EXIT IF ENCLOSED, FROM TOP IF OPEN N/A N/A N/A

AUGER

AUGER

FOUR SHOVEL OR SHOVELS, AUGER ONE FROM EACHSIDE

Screw conveyors

transfer

sludge-type

materials

(such as ash effluents) and are usually

enclosed

systems.

Theoptimum

sampling

point for these systems is the content

exit.

If this point is located

in an unreachable position, the sample

must then be Withdrawn

from the entrance

or exit area, depending on whether

the stream

is influent

or effluent

using a pipe, thief

or auger technique

(Section

6.3.2).
Duct conveyors

consist

of either

gravity

feed systems

or chaindrive scrapers and may be open top or enclosed

depending

on the fineness

of the solid being transported.

Open duct conveyors

are sampled

by removing

one shovelful of material

from the top from the adjoining

catwalk.

Closed

ducts

are sampled

by taking

one shovelful

from the exit point.

If these points

are unreachable,

the sample

must be taken from the storage

pile using a pipe, thie• or auger (Section

6.3.2). 6.3.2 Boring

Techniques

(References

22, 46, SO) Pipe borers

represent

another

class of solid sampling

methods

applicable to materials

stored

in piles,

silos or bins.

The pipe is inserted

into the material t• be sampled

at regular

intervals.

The method

is fairly

reliable, providing that the pipe is long enough

to reach the bottom

of the material. However, it is only applicable

to fine or powdered

dry materials,

because 78lumps

or any stickiness

will jam or plug the pipe.

Small pipe borers

can be used to sample

material

in sacks or cans.

There are primarily

two pipe designs that give best results,

One is a simple

pipe that is tapered

so the end first inserted

is smaller

in diameter

than the handle

end. A more :sophisticated design,

known as a thief,

makes the sample

more representative vertically. It consists

of two close-fitting

concentric

pipes sealed

at the base in a conical

point.

Longitudinal

slots are cut along the side of each pipe.

The thief is inserted

with the slots turned

away•from

each other and then, when the sampler

is in position,

the outer pipe is rotated,

lining up the slots and allowing

the inner pipe to fill with sample.

For proper results with any design

of pipe borer,

the.opening

through

which the sample material passes

(slots or circular

pipe •nds) must be larger

than the largest particle

size. Auger samplers,

a form of drill,

pack the sample

in the helical

groove of the auger and can be enclosed

in a casing

if the nature

of the sample

is such that it will spill when the auger is removed

from the.hole.

Like pipe borers, they are simple

to use and have the further

advantage

of being applicable to a greater

variety

of materials.

For example•

augers

work well for materials

that are packed

too hard for the insertion

of a pipe sampler. For very packed

materials,

machine-driven

augers

are available. However, if spillage

is a serious

problem,

a thief type pipe sampler

is the better

choice. 6.4 SAMPLE

COLLECTION

AND STORAGE

(References

3, 20, 22, 50) It is always

preferable

to sample

a moving

stream

either

in pipes or off conveyor

belts rather

than stationary

storage

sites.

This isparticularly true if the sample

has a wide particle

size distribution.

Stored containers or heaped

beds of m•terial

tend to settle,

segregating

theparticles according

to size and density,

and it is difficult

to compensate

for this bias during

sampling.

Furthermore,

large masses

of stored

material
are extremely

difficult

to handle.

The interio•

portions

are relatively inaccessible, and the amount

of time and space needed

to move the material enough to take a representative

sample

can become

prohibitive.

However, such situations

can generally

be avoided

by a good sampling

test plan.
7 ̧9Typically in a process

test for trace elements

the solid materials of interest

are the feed materials

and the residues

from particulate

matter scrubbers such as baghouses,

high energy

venturis,

and electrostatic

precipitators. Raw feed stock as it passes

through

the process

stream

may pick up other materials

as contaminants

and therefore

differs

greatly

in composition from the final feed to the process.

Consequently,

samples should be taken at the last possible

site before

the stream

is fed into the process. This means that sampling

will generally

be conducted

from a feed hopper, if accessible,

or from the pipes or conveyors

which feed the materials to the process.

Similarly,

scrubber

residues

can be sampled

from thecollection hopper

o6 from pipes going to the hopper.

Extra handling

steps only increase

the chances

of the sample

becoming

contaminated. When samples

are taken from conveyor

belts,

the standard

procedure

is to stop the conveyor

at regular

intervals

(e.g., every 10 or 15 minutes) and shovel

off a section

of the material.

Flat-nosed

shovels

with straight perpendicular sides are best for this type of sampling. Samples collected

in accordance

with the above prescribed

procedures should be stored

in air-tight,

high density

polyethylene

containers

until ready for analysis.

Large samples

should

be placed

in metal containers lined with polyethylene

bags.

80CHAPTER Vll LEVEL 1 INORGANIC

ANALYSIS

TECHNIQUES

7.1 INTRODUCTION

(References

1, 2, 51) Sampling and analytical

programs

can at a minimum

be divided

into three distinct

categories.

The first category

is compliance

testing where the procedures

along with their precision

are delineated

in the Federal Register.

A second

type of sampling

and analytical

program

is designed to support

specific

R&D programs

and the precision

and accuracy of the data are defined

by its end uses.

The third type of program

is designed to provide

information

which can be utilized

in each of the specific levels

of a phased

environmental

assessment.
In respect

to the Level I environmental

assessment

as described

in this manual,

a goal for precision

and accuracy

within

a factor

of two to three of the rate of input and emission

composition

is desired. achieve this goal, the analytical

results

must have an accuracy•f

-50 to +100 percent

assuming

a sampling

accuracy

of -50 to 100 percent

(Section

1.5). Samples obtained

in accordance

with the procedures

outlined

in the preceding chapters

will be either

gases,

liquids,

or solids.

Themultimedia analysis

flow scheme

presented

in Figure

24 represents

the way in which each of the sample

types is split for organic

and inorganic

analysis. The inorganic

analysis

scheme

is detailed

in a companion

flow diagram (Figure 25).The analytical

methods

chosen

for this manual

are the recommended techniques for Level 1 determinations. They represent

the optimum

approach to an integrated

multimedia

assessment

effort

and should

be considered comprehensively rather

than independently.

For example,

on-site

GC is identified for general

Level I inorganic

gas analysis.

Viewed

independently,

a variety

of alternative

techniques

will provide

satisfactory

Level 1 data for inorganic

gases;

yet within

the integrated

Level I analysis

format, the GC can also be used for organic

gases and consequently

becomes

the optimum choice.

81 ̧82-7-

83Level i samples

are analyzed

without

making

assumptions

regarding the content

of any given sample.

Consequently,

the analysis

plan is designed to create

a network

capable

of screening

all incoming

samples

in such a way that no environmentally

significant

element

or species

escape undetected. This "screening

network"

applied

to Level I inorganic

analysis is designed

to detect:

• Inorganic

elements

in all influent

and effluent

streams,

• SO2, NOx, CO, 02, C02, N 2, H2S, COS, NH3, HCN and (CN)2 in gaseous streams,

• pH, acidity,

alkalinity,

conductivity,

BOD, COD, dissolved oxygen, dissolved

solids,

and suspended

solids

in water streams in addition

to inorganic

elements,

and

• Leachable

cations

and anions

from samples

which are solids (particulate matter

from SASS, slurry

solids,

etc.)
In this way, environmentally

important

components

or streams

are identified and prioritized

so that the Level 2 effort

can be directed

to the most environmentally significant

streams. The following

sections

in this chapter

describe

special

considerations in the analysis

of Level 1 samples. 7.2 LEVEL 1 ANALYSIS

METHODOLOGY The analysis

of samples

from the Level i sampling

effort

will require the use of methods

applicable

to gases,

liquids

and solids.

Solids

and liquids will be analyzed

for elements

including

the halogens

by spark

source mass spectrometry

(SSMS)

after the proper

sample

preparation. Liquids will be analyzed

directly

for complex

anions

using reagent

test kits (Hach or Bausch

and Lomb) either

in the field or in the laboratory (see Table 3, pg. 75). These same reagent

kits will

be used to analyze the leach solutions

from the solid samples.

Gas samples

will be analyzed

on site for inorganic

components

by gas chromatography

(GC I. The following paragraphs discuss

the application

of these analysis

approaches

to the samples collected.

847.2.1 Elemental

Analysis

by Spark Source

Mass Spectrometry (References 52 through

62) There are two general

types of SSMS detection

systems:

photographic plate, and electrical

detection.

For Level 1 survey

purposes,

thephotographic system

using the "just disappearing

line"technique

will be applied. To achieve

the highest

sensitivity,

a series

of exposures

of the photoplate is made using the sample,

fol.lowed

by a series

of exposures

with areference sample.

Precision

and accuracy

are highly

dependent

on spectral

line widths and shapes.

These parameters

define

optical

densities

which are converted to ion densities

by means of calibration

curves.

A number

of computer-oriented systems

for the derivation

and integration

of ion intensity profiles have been developed

for use in accurate

and precise

determinations.
Four specific

groups

of samples

for inorganic

element

analysis

result from a Level 1 sampling

survey: 1) XAD-2 trap, 2) Aqueous

samples, 3) Organic

samples

(liquid

or solid),

and 4) Particulate

matter,

including

probe and cyclone washes and ash samples.
In order to analyze

these samples

for trace elements

by SSMS, two general sample

conditions

must be met: 1) The sample,

if it is not a conductor,

must be placed into a conducting

medium

(graphite),

and 2) The sample

must be as free as possible

from organic matter which can complicate

spectra

interpretation. Figure 26 shows in schematic

form how each sample

type is prepared

to meet these conditions;

further

explanation

is given In the following paragraphs.Aqueous liquid

samples

can meet the two conditions

simply

by adding a small amount

of the sample

to powdered

graphite

and allowing

the water to evaporate.

(One ml of solution

is needed

to obtain

a i ug/l sensitivity assuming a basic SSMS sensitivity

of 10"9g.)

The graphite

is then pressed into an electrode.

Particulate

matter,

ash, and fuels will require

more86extensive preparations

consisting

of reducingthe

organicmaterial content

of the matrix.

This matrix

reduction

step consists

of ashing

the sample

by Parr bomb combustion

of the sample

over HNO 3. An aliquot

of this sample

is then formed

into an electrode

in the. same manner

as the aqueous

samples. Analysis of the XAD-2 sorbent

trap for trace elements

is a unique problem because

little

is known about volatile

element

retention

of the sorbent trap.

In addition,

adsorption

is not uniform

throughout

the length of the trap.

For this reason,

the XAD-2 sorbent

is first thoroughly

mixed to ensure

a homogeneous

sample,

and then a 2-g aliquot

of the sorbent

is used in a Parr bomb combustion

over HNO 3. The inorganic

elements

are then determined by SSMS, and the remainder

of the sample

is then used for organic analys'is (Chapter

VIII.) 7.2.2 Wet Chemical

Analysis

for H• As and Sb (References

63• 64) While SSMS can theoretically

analyze

any element,

it has been found in practice

that Hg, As, and Sb are analyzed

poorly

by SSMS.

Thus, these elements are determined

by atomic

absorDtion

spectroscopy

(AAS) or wet chemicals methods.

Figure

27 summarizes

the analysis

scheme

for Hg, As, and Sb for each of the four general

types of samples.

This scheme

presents the dissolution

techniques

for the various

samples

so that once the sample is in solution,

the appropriate

AAS or colorimetric

procedures

can be performed.Since

several

additional

sample

preparation

steps are included

in the analysis scheme,

care must be taken to avoid contamination.

Clean working

areas set aside for trace material

analysis

are required.

Reagent

blanks

on all solutions,

acids and reagents

must be run to ensure

accurate

results. Analysis of water,

particulate

matter,

ash and fuels for Hg, As,;and Sb is accomplishedwith well known analysis

schemes.

In the •D-2analysis, the samples

are treated

as fuels and bomb combusted.

These analyses have few in.terferences.

87o

oo

887.2.3 Gas Chromatographic

Analysis

of Gaseous

Components Gaseous samples

to be analyzed

will come from various

sources including:

•

•

•

•

• Stacks•,Vents,Process

input streams, Process product

streams,

and Ambient air. These samples

must be analyzed

for both inorganic

and organic

species

over a span of concentrations

ranging

from sub-ppm

levels

for sulfur

compounds to several

percent

for CO 2 and water in stack gas effluents. Because many of the samples

which are taken,

especially

those whichcontain H2S and other sulfur

species,

are unstable

due to wall absorption

or possible chemical

reaction,

it is recommended

that the GC analysis

be performed on site.

This also eliminates

the shipping

of a potentially large number

of bulky sample

containers

and permits

additional

sample taking if a problem

area is identified. Recent advances

in gas chromatography

have led to the development

of sensitive and compact

instruments

that are practical

for field applications. In addition,

multidetector

units such as those manufactured

by Meloy, Beckmann, Tracor

and others

expand

the scope of analYsis

to include virtually all gaseous

species

without

having

a van full of gaschromatographic units.

It •s recommended

that a multidetector

unit capable

of detecting sulfur

compound

at the ppb level be purchased

for anenvironmental assessment

van. Because no single

unit is suitable

for all proposed

analyses,

a set of columns,

temperatures,

and detectors

is shown in Table 5. Organic species are shown because

they will be present

in most samples

along with the inorganic

species.

It is not expected

that the proposed

set ofconditions will be suitable

for all mixtures

and all possible

concentration ranges. If a unique

situation

should

arise,

an alternative

set of analysis conditions should

be selected

and submitted

tO the project

officer

and PMB-IERL-EPA for approval. 899OThe actual

on-site

analysis

will be accomplished

by using an evacuated vessel to sample

the port, vent, or ambient

air• This vessel

will then be returned to the mobile

van and attached

to the gas chromatograph

via an automatic gas sampling

valve.

The sampling

vessel

will automatically

be sampled and the gas analyzed

on the GC. The vessel

can then be stored

for further analysis

back at the laboratory

or purged,

cleaned

and evacuated for further

use in the field. 7.2.4 Analysis

of Nitrogen

Oxides Two gases of environmental

interest

(NO and NO 2) are not measured routinely On a gaschromatograph. The Level 1 analysis

of NO/NO 2concentrations will be performed

using the chemiluminescence method.

Although this is a state-of-the-art analysis

technique,

it is substantially

less labor-intensive than EPA Method

7. This method

as adapted

to Level 1 analysis involves

admitting

gas samples

into a 3-1iter

evacuated

flask,

as described in Chapter

II. The sample

is then transported

to the instrument and analyzed.

Because

a major portion

of the analysis

time on the instrument involves

calibration,

it is recommended

that only sufficient calibration to maintain

a minimum

accuracy

of ± a factor

of 2 (+100percent, -50 percent)

be performed. 7.2.5 Analysis

of Leachable

Material

(Reference

25• The analysis

of water and HCI leachable

material

from solids

can be performed by the standard

procedures.

Spark source

mass spectrometry

will be used for elements,

halogens,

and total sulfur,

while reagent

test kits will supplement

SSMS by performing

a variety

of tests for complex

anion species.7.2.6 Analyses

Specific

for Aqueous

Samples •References 37, 65, 66, 67,

68, 69)

• In addition

to the general

inorganic

elemental

analysis

specified

in this chapter

and the organic

analysis

specified

in Chapter

VIII, thefollowing analyses

must be performed

on all aqueous

samples:

• Acidity

• Alkalinity

• .pH

• BOD

• COD 91• Conductivity

• Total dissolved

solids

• Anion analysis

for SO 4 • Total suspended

solids

• Dissolved

oxygen

• Ammonia

• HCN NO2-/N03-,

and CO 3

All these analyses

can be performed

either

in the field or thelaboratory using reagent

test kits, although

practicable

considerations

will usually indicate

that all analyses

except

BOD, COD, and suspended

solids will be done in the field.

These kits, which are manufactured

by Hach or Bausch and Lomb, use a series

of procedures

that usually

follows

amodified and simplified

version

of standard

methods.

The reagents

areencapsulated and stored

in smaYl plastic

pillows

in pre-measured

quantities until opened

fo• analysis.

Upon addition

of the reagent

or reagents

to the sample,

component

concentrations

are determined

colorimetrically or turbidimetrically using reference

color discs or portable

photometers.

In some cases endpoint

titrations

are used.

Although

they are not as accurate as the standard

laboratory

procedures,

they have sufficient

accuracy

for Level I objectives

and provide

the following

advantages

which qualify

them for Level 1 survey

use: Sample preservation

The need for involved

sample preservation schemes

is eliminated

by on-site analysis.

• Storage

space

The need for large areas for sample storage is eliminated. Simplicity The reagent

test kits are designed

to be used by non-technical

personnel. On-site analysis

This points

out specific

problem areas allowing

more detailed

sampling

by the survey team, if necessary. When used in the•aboratOry

for analysis

of leachables, they provide

quick,

inexpensive

analyses

for the required data.

92CHAPTER Vlll LEVEL 1 ORGANIC

ANALYSIS

TECHNIQUES

8.1 INTRODUCTION In order to ensure

that important

emission

problems

do not go undetected, and at the same time to allow the evaluation

of a large number of sources

in a cost effective

manner,

a simple

set of analytical

survey methods is presented

in this chapter.

Rather

than to represent

acomprehensive analysis,

the objective

of these Level I procedures

is to provide

an estimate

of the predominant

classes

of organic

compounds

present

in a given sample.

As a result,

the methodology

is designed

to determine

the presence or absence

of all major classes

of organic

compounds

within

the factor of two quantitative

objectives

of the Level I analysis.

Inaddition, these methods

can be performed

in most laboratories

and by a technical staff with limited

previous

experience. Samples obtained

in accordance

with the procedures

outlined

inChapters II through

VI will be either

gases,

liquids,

or solids.

Themultimedia analysis

flow scheme

presented

in Figure

28 shows how each of the sample types is split for organic

analysisr 8.2 LEVEL 1 ORGANIC

ANALYSIS

METHODOLOGY An overview

of the methodology

to be used for the Level I organic analysis is shown in Figure

29. This methodology

deals with thepreparation of the samples

to provide

a form suitable

for analysis,

and with their subsequent analysis.
As indicated

in Figure

29, the extent

of sample

preparation

required varies with sample

type.

The low molecular

weight

CI-C 6 hydrocarbons

are determined by gas chromatography

on site and require

no preparation. Organic liquids,

such as fuel oils, Will not need pretreatment

and are placed directly

into the analysis

scheme.

However,

the majority

of the samples, including

the SASS train components,

aqueous

solutions

such as scrubber waters,

and bulk solids

such as coal or slag, require

extraction with solvent

prior to analysis.

This extraction

separates

the organic portion of the samples

from the inorganic

species

and allows

analysis

to )roceed without

complication.

The analysis

of organic

extract

or organicSAMPLE PREPARATION ANALYSIS

= z•o

94FOR

C1-C 6 HYDROCARBONS

ALIQUOT FOR CI-CI2 HYDROLIQUIDS

ORGANIC ANALYSIS

SOLUTIONS MATERIALS

ALIQUOT(R 600 rag)

LIQUID CHROMATOGRAPHI SEPARATION

Figure 29. Level 10rqanic

Analysis

Flow Diagram

95liquid then proceeds

by first taking

an aliquot

of the sample

or extract for direct

GC analysis

of compounds

boiling

in the range of C7-C12

hydrocarbons (I00-200°C).

Then an infrared

(IR! spectrum

is obtained

on the second aliquot.

This IR spectrum

provides

an indication

of the types of functional groups

present

in the sample

and also provides

a control

check point for subsequent

analyses.

All functional

groups

identified

in this total sample

must be accounted

for in the succeeding

steps. The sample

extract

or organic

liquid

is separated

by silica

gel liquid chromatography (LC), using a solvent

gradient

series,

into eight fractions of varying

polarity.

The weight

of each of these fractions

is obtained

so that one can determine

the distribution

of the sample

by the various

class types. An IR spectrum

is then obtained

on each LC fraction

fordetermination of the types of functional

groups

present.

A low resolution

mass spectrum (LRMS) is also obtained

on all fractions

which exceed

theconcentration threshold

criteria

in order to determine

the principal

compound types present

in each fraction.

For the sample

streams

identified

in the Level i scheme,

these concentrations,

computed

back to the source,

are:

• Gas (particulate,

sorbent

trap, etc.)

0.5 mg/m 3

• Solids I mg/kg

• Solutions 0.1 mg/l
Care must be taken in this computation

to correct

for those C7-C12 compounds that wereanalyzed

by GC and not lost in the LC concentration step. It should

be emphasized

that sample

contamination

and solvent

impurities

are common

problems

in organic

analysi

s The best possible

laboratory

procedures must be used along with verified

pure solvents.

Blanks

and controls should be run for each stage in the analysis

scheme. 8.3 SAMPLE

PREPARATION This section

presents

sample

preparation

procedures

that are appropriate for most samples.

The specific

solvents

indicated

should

be used where possible. In the case of unusual

sample

requirements,

an alternate

procedure should

be selected

and presented

to the project

officer

and the Process Measurements Branch,

IERL-RTP,

for approval.

An aliquot

of sample

extracts will be set aside fo.r direct

gas chromatographic

analysis

of. materials

in 96the

C7-C12

boiling

range•

It is necessary

to obtain

the total weight

of organics inthe

solvent

extract,

to obtain

an IR on a portion

from this extract, and to concentrate

the extract

for the LC separation.

Theappropriate stage at which to conduct

each of these steps (gravimetric

analysis, IR, concentrate)

will depend

on the quantity

and solubility

of the sample. When possible•

it is recomended

to have at least 10 mg of sample

for the gravimetric

analysis.

Prior to the LC analysis

step, it isrecommended that the solvent

solutions

be concentrated

to i to 10 ml. The Kuderna-Danish apparatu

s for volumes

less than one liter is recommended for sample

concentration,

and a rotary

evaporator

is recommended

for volumes which exceed

this amount. 8.3.1 Aqueous

Solutions Extraction of aqueous

solutions

should

be carried

out with methylene chloride using a standard

separation

funnel

fitted

with a Teflon

stopcock. If necessary,

ammonium

hydroxide

or hydrochloric

acid should

be used to adjust

the pH of the water to neutral

before

extraction.

Normally, three 500-ml methylene

chloride

extractions

of 10-1iter

samples

should

be sufficient. 8.3.2 Solids•

Particulate

Matter

and Ash All solid material

including

products,

raw materials,

cyclone,

probe and filter

particulate,

and ash should

be extracted

for 24 hours with methylene chloride

in a Soxhlet

apparatus.

The Soxhlet

cup must bepreviously extracted

in order to avoid contamination.

COver the sample with a plug of glass wool during

the extraction

to avoid carry-over

of the sample. 8.3.3 Sorbent

Trap The XAD-2 resin from the sorbent

trap is extracted

with pentane. After the resin is removed

from the SASS train cartridge,

homogenized,

and a 2-g portion

is removed

for the inorganic

analysis,

the balance

is extracted to remove

the organic

material.

A large Soxhlet

extraction apparatus, available

from several

manufacturers,

must be used tO extract the 400 ml of resin.

The resin is then transferred

to a previously

cleaned extraction thimble

and secured

with a glass wool plug.

Approximately

972

liters

of pentane

is added to the 3-1iter

reflux

flask.

(The dumping volume of an appropriate

commercial

extractor

is 1500 ml.) The resin is extracted for 24 hours.

The boiling

pentane

in the flask should

be examined periodically to determine

whether

additional

solvent

is needed

to replace that lost by volatilization. If large quantities

of polar materials

are extracted,

they mayprecipitate in the boiling

flask near the completion

of the extraction.

Addition of cool methylene

chloride

to the flask,

after extraction

is complete,

will simplify the subsequent

transfer

and analysis

steps. The XAD-2 resin should

not be extracted

with methylene

chloride

in the Soxhlet

apparatus

because

the compatibility

of this resin with methylene chloride has not been fully evaluated. 8.4 ANALYSIS

OF SAMPLES

FOR ORGANICS The analysis

of each of the prepared

or isolated

samples

for organic compounds follows

the scheme

introduced

in Figure

29. The overall

scheme is based upon an initially

recommended

scheme

(Ref. 51) which has been revised based upon subsequent

laboratory

evaluations

(Ref. 70). The LC/IR/LRMS

procedure

will provide

reliable

data on the compound types present

in the samples

for the relatively

high boiling

compounds. Unfortunately, the SASS train will not capture

(and retain

for analysis) the organic

compounds

with boiling

points

in the CI-C 6 range (up to 70°C); and the volatile

materials

in the C7-C12

range (lO0-200°C)

are lost in various degrees

in the sample

concentration

steps required

for the full analysis. Consequently,

separate

gas chromatography

procedures

have been devised for the analysis

of these two ranges

of materials. 8.4.1 Gas Chromatographic

Analysis

of C l C 6 Range (Ref. 71 through

75) The on-site

gas chromatographic

requirements

for analysis

of the C I C 6 gases was presented

in detail

in Table 5 in Chapter

VII. For organic analysis

the GC system

should

be calibrated

for retention

time and quantity with a C 1 C 6 n-paraffin

mixture. The conditions

recommended

for this analysis

are: Column: Porapak

Q, 100/120

mesh, 6' Detector: Flame Ionization Temperature: Isothermal

at 100°C981The

temperature

calibration

curve is prepared

in the•standard

manner (Ref. 75). The GC system

will simply

be separating

and analyzing

mixtures of materials

with a given boiling

point range (and polarity

in some cases), rather than individual

pure •ompounds. hydrocarbons are:

Gas • Methane, C 1 -161-88 Ethane C 2Propane, C 3 -42. Butane, C 4 0 Pentane, C 5 36 Hexane, C 6 69 The boiling

points

of the C 1 C 6

However, since the chromatogram

peaks will represent

mixtures

of materials present in a certain

boiling

range,

rather

than pure, individual

compounds, it is recommended

that material

observed

in the chromatogra•

be reported

as present

in the ranges

given below:

1

-160 to -100 2 -100 to -50 3 -50 to 0 4 0 to 30 5 30 to 60 6 60 to 90 If, from other information,

it is thought

that the species

being analyzed are solely

the C I C 6 hydrocarbons,

the basis of the data may be reported

as such and the chromatogram

peaks ass;'gned

accordingly.

998.4.2 •as•Chromatographic Analysis

of C 7 CI? Range The samples

used for this analysis

are the methylene

chloride

and pentane extracts

before

concentration,

and the neat organic

liquids. Organic species

boiling

in the range of the C 7 C12 hydrocarbons

which would otherwise

be lost by evaporation

can be analyzed

in a manner

similar to that described

above for the C 1 C 6 gases.

The major difference

is the solvent

interference

and GC requirements.

Even for the dilute

sorbent trap extracts

a flame ionization

detector

is sufficiently

sensitive

for analysis to require

only a one-microliter

sample. The conditions

recommended

for this analysis

are: Column: 1.5% 0V-I01

(or SE-30)

on GasChrom

Q, i00/120

mesh, I/8" OD x 6' SS Detector: Flame ionization Temperature Program:

Isothermal

at 50°C for 5 min., then program at lO°C/min

to upper limit of 150°C. The initial

isothermal

portion

of the temperature

program

is required

to allow the solvent

to elute prior to the C 7 hydrocarbon.

It will probably be desirable

to prepare

solutions

of the neat organic

liquids

in order to prevent overloading

and degradation

of the column. The basic calibration

and reporting

requirements

are the same as for the C 1 C 6 gases.

The boiling

points

of the hydrocarbons

and recommended reporting ranges

are: vapor

Bp (oc) Heptane, C 7 98 Octane, C 8 126 Nonane, C 9 151 Decane, C10 174 Undecane, C11 196 Dode•ane, C12 216 789lOII12

90 to llO .110 to 140 140 to 160 160 to 180 180 to 200 200 to 220 SinCe the numbers

of possible

compounds

in these ranges

are very large, it is recommended

that material

and its quantity

simply

be reported

as

IO0being

present

in these rangeS.

Any specific

compound

assignments

should be supported

by confirmatory

data and may be beyond

the scope of the Level 1 analysis. 8.4.3 Liquid

Chromatographic

Separation The detailed

procedure

for the liquid

chromatographic

(LC) separation is given in Appendix

C. All sample

extracts

and neat organic

liquids

are subjected to this procedure,

if sample

quantity

is adequate.

A 100 mg portion of the sample

is preferred

for the LC, but smaller

quantities

down to a lower limit of about 8 mg may be used.

The sample

is separated

into approximate classes

on silica

gel using a gradient

elution

technique.

The solvent sequence

used for the procedure

is given in Table 6.

Fraction No.I2345678

Table 6. Solvents

Used in Liquid Chromatographic Separations
Solvent Composition Pentane20%' Methylene

Chloride

in Pentane 50% Methylene

Chloride

in Pentane Methylene Chloride 5% Methanol 20% Methanol 50% Methanol 5/70/30, Conc.in Methylene

Chloride in Methylene

Chloride in Methylene

Chloride HCl/Methanol/Methylene

Chloride
The LC Separation

procedure

is not a high resolution

technique

and consequently there is overlap

in class type between

many of the fractions. Fraction 1 contains

only the paraffins

and possibly

some olefins.

Fractions 2 through

4 contain

predominantly

aromatic

species.

The smaller aromatics (benzene,

naphthalene)

will tend to elute in the early fraction (2) while the larger

aromatics

(benzpyrene,

etc.) will tend to elute in Fractions 2 through

4. Some low polarity

oxygen

and sulfur

containing species may also elute in Fraction

4 but most of these will not elute until addition

of methanol. i01Fractions 5 through

7 will contain

the polar species

including

phenols, alcohols, phthalates,

amines,

ketones,

aldehydes,

amides,

etc. Thedistribution of class type between

Fractions

5 through

7 will be a function

of their polarity and affinity

for the silica

gel. Some weakacids

may elute in Fraction 7.The very polar species,

primarily

acids such as carboxylic

acids and sulfonic acids,

will elute in Fraction

8. After each fraction

is collected,

it should

be transferred

to a tared aluminum micro weighing

dish for evaporation

and gravimetric

analysis. Fraction 8 should

be dried in a glass container

because

of its hydrochloric acid content.

Each fraction

is subsequently

analyzed

by IR and, when the quantity is sufficient,

LRMS (see Section

8.4.5). 8.4.4Infrared AnaIxsis The total sample

extract,

or neat liquid,

and the

eight LC fractions

are analyzed

by infrared

(IR) spectrophotometry. IR spectra

are obtained

on KBr salt plates

using methylene

chloride

to transfer

the sample

to the plates. A grating

spectrophotometer should

be used.

Sample

quantity

is adjusted so that the maximum

signal

of the strongest

peaks •s about 10% transmission. The transmission

Signal

of the most intense

peak should not be less than 10%. Spectra are interpreted

in terms of functional

group types present

in the sample

or LC fraction.

The many reference

texts (Ref. 76 through

79) in this area are of considerable

help in interpreting

theiR

spectra. 8.4.5 Low Resolution

Mass Spectrometry
Low resolution

mass spectra

(LRMS) are obtained

on each LC fraction which has sufficient

quantity,

when referenced

back to the source.

For the various

samples.those

quantities

are: Gas SASS train samples Ambient air Particulate Ambient air Sorbent

trap SolidsAqueous solutions O.5mg/m

3
I ug/m 3
0.5 mg/m 3
I mg/kg0.1 mg/1 102,The

mass spectrometer

should

preferably

have a resolution

(m/Am) of 1000, batch and direct

probe inlet,

variable

ionizing

voltage

source

and electron multiplier

detection.

Volatile

samples

are analyzed

by insertion in the batch inle:t.

It is anticipated,

however,

that most samples

will require analysis

via the direct

insertion

probe.

A small quantity

of sample is placed

in the probe capillary

and inserted

into a cool source. The temperature

is then programmed

up to vaporize

the sample.

Spectra

are recorded

periodically

throughout

this period.

Spectra

are normally obta•ned at 70 ev ionizing

voltage,

but low voltage

(10 ev) spectra

may be much simpler

in some cases.

Spectra

may be obtained

at both high and low voltage dictated

primarily

by the spectra

obtained. Interpretation of the spectra

is guided

by knowledge

of the LCseparation scheme,

the IR spectra,

and other information

about the source.

Data

are grouped

by homologous

series

based on a most probable

structure

assignment. Molecular

ion series

and fragment

ions help to identify

compound classes. Polynuclear

aromatic

hydrocarbons

are characterized

by intense double ionization.

Many other factors

go into the interpretation

of the spectra guided

by the sample

itself,

experience,

and literature

references. The compilations

of reference

spectra

(Ref. 80 through

83) are particularly helpful in the task of reducing

the LRMS data.

103CHAPTER IX PARTICLE MORPHOLOGY

AND IDENTIFICATION
9.1 INTRODUCTION Level i particle

morphology

and identification

use techniques designed to study the physical

(including

structure)

and chemical

properties of individual

particles

so that qualitative

information

concerning the potential

health

effects

of the collected

particulate

matter

can be determined. An environmental

assessment

effort

generates

particulate matter samples

from the SASS trains

and from high volume

samples

collecting fugitive

emissions.

An important

part of the morphological

examination of particulate

matter

is the identification

of contributing

sources, e.g., fly ash, bottom

ash, coal dust, catalyst,

etc., so that a detailed Level 2 particulate

matter

sampling

effort

can be planned. The Level 1 effort

described

in this chapter

is based on field weights and microscopic

techniques

which include

photomicrography, particle

size distribution, and polarized

light micrography

(PLM).

• Field weight

Preliminary

weights

will act as acontrol for contamination

and/or

loss of sample.

• Photomicrography Field or laboratory

photographs will provide

sample

control

and stability

checks during shipping

and handling

and will provide

preliminary visual

identification

of particles

and particle characteristics. (It is recommended

that a color photomicrograph

be taken in the field for documentation of the sample

and its stability).

• Size distribution

Size distribution

of fugitive emissions particulate

should

be determined

using the photomicrograph.

• Polarized

light micrography

(visual

identificati'on) Using polarized

light._(R•f"

84, 85, 86• the particu- late matter

is viewed

under a microscope;

particles down to 0.5• can be identified

by •hysical

appearances. Although the procedures

described

in this chapter

are straightforward, they do require

a degree

of skill,

experience

and the ability

to makeconsistent subjective

evaluations

on the part of the personnel

performing

the work. Component

identification

should

be carried

out by a trained

technician and/or

microscopist

either

internally

or in a commercial

laboratory ,i104specializing in the procedures

described

in this chapter.

The same personnel

or commercial

laboratory

should

be used for each individual

or series

of environmental assessments.

In either

case, cost guidelines

such as those in Reference

i or as specified

by the projectofficer

should

be followed

so the cost of the microscopic

analysis

does not exceed

its utility. 9.2 PARTICLE

CHARACTERIZATION Figure 30 presents

a flow chart for the Level 1 identification

and Characterization of unknown

particles.

The tests indicated

in thefigure should

be performed

in conjunction

with the macro inorganic

and organic tests performed

on the complete

sample

fractions

(see Chapters

VII and VIII). To obtain

a maximum

amount

of information

from a given sample,

a detailed discussion of particle analysis by microscopy

can be found in Ref. 84. 9.2.1 Handling

Particles

for Microscopic

Examination Whenever the particulate

sample

is handled,

care must be taken to avoid contamination

or mutilation.

The mounting

of the sample

should

be performed in a dust free environment.

Furthermore,

for sizing

purposes, any manipulations

that would grind or crush the sample

should

be avoided. Although the mounting

of particulate,

matter

from the cyclones

is straightforward, the material

collected

on filters,

especially

if matted filters are used, can cause several

problems.

Care must be taken to ensure that any removal

process

does not dislodge

any of the filter

material.

In many cases,

the quantity

of particulate

matter

collected

on the filter material may be small and difficult

to remove.

If a sufficient

layer of particulate matter

is collected

so that a small (1-10mg)

quantity

can be scraped off, then a complete

microscopic

analysis

can be performed.

If the particles cannot

be removed

from the filter,

only a photomicrograph

for quality control

and preliminary

visual

identification

can be taken. 9.2.2 Photomicro•raphy and Particle

Sizing

for Fugitive

Emissions After the particulate

matter

has been mounted,

a color photomicrograph is taken to identify

the sample

and to check chemical

stability.

This photograph will be part of the documentation

that accompanies

the sample

as it is logged

and stored.

If long periods

of time occur between

sampling and analysis,

the original

photomicrograph

is compared

to a recent

one to determine if any physical

change

has occurred

in the sample. 105106The microphotographic procedure

is thoroughly

discussed

in Ref. 84. In all cases,

the exact conditions

used (lighting,

magnification,

mounting liquid, etc.) should

be noted so future

comparisons

involve

the samephotographic conditions. Since particles

are irregularly

shaped,

the term "diameter"

is really not applicable

in descriptions

of particle

size.

Two general

approaches have been developed

to approximate

the measurement

of this parameter.

The projected diameter

is the diameter

of a circle

equal in area to the profile of the particle

when viewed

normal

to the positions

of greatest

stability (Ref. 87). The statistical

diameter

takes some average

linear

measure

of the projection

of the particle

in a fixed direction,

assuming

the particles

are randomly

oriented

(Ref. 88). Statistical

diameters

can be measured

as the mean distance

between

two tangents

on Opposite

sides of the particle image (Feret's)

or the mean length

of a line that intercepts

the particle image and divides

it into equal areas (Martin's). The selection

of the precise

method

of diameter

measurement

is not well defined.

The projected

diameter

corresponds

closely

to sedimentation measurements (Ref. 88), while Feret's

and Martin's

diameters

are slightly greater and less than the p•ojected

diameter,

respectively.

For a more detailed discussion

of the procedures,

the reader

is directed

to Ref. 88. 9.2.3 Visual

Identification In many cases,

the trained

technician

can identify

particulate

matter by visual

observations

and comparison

to known samples

using polarized light micrography

(Ref. 84). Particles

are first viewed

dry mounted

with top lighting

and the crystal

shape or structure

is observed.

The shape, the col or, and cleavage

of the crystals

and other visual

characteristics

are together

used to identify

or narrow

the list Of possible

compounds.

107CHAPTER X BIOLOGICAL TESTING
I0.1 INTRODUCTION Biological

testing

must be considered

an integral

part of the phased approach to environmental

assessment.

Although

the primary

emphasis

in this and related

documents

(Ref. 1, 2, 3, 22, 25,

27, 45, and 51) is on traditional chemical

and physical

tests,

biological

(bioassay)

tests are required in order to provide

direct

evidence

of complex

biological

effects such as synergism,

antagonism

and bioavailability. Since in most cases, this information

cannot

be derived

from physical

and chemical

tests on samples consisting

of complex

mixtures,

biological

testing

will beincorporated into all three levels

of the phased

environmental

assessment.

As applied to Level 1, biological

testing

is limited

to whole sample

testing which is consistent

with the survey

nature

of this level.

Biological

testing on fractionated

samples

or on specific

components

of a given sample involves a certain

degree

of quantification

that is more appropriate

to Level 2 or 3 testing. At present,

specific

biological

test procedures

have not beencompletely identified

and, therefore,

cannot

be incorporated

into the manual. Thus, although

bioassy

testing

has been identified

in Figures

1 and 2 (Chapter I), exact testing

requirements

have not been consistently

delineated in the detailed

flow diagrams

presented

in Chapters

II-VI.

It should

also be noted that the samples

size specified

in Table 1 (Chapter

I) may be modified when the exact biotesting

procedures

are identified. The EPA's Office

of Health

and Ecological

Effects

(OHEE) is presently developing detailed

bioassay

requirements

and test procedures,

and it is expected that the initial

recommendations

will be available

in August,

1976. Moreover, a Level l bioassay

procedures

manual

similar

to this manual

will be issued in January,

1977.

The following

sections

discuss

the types of tests and the scope of the manpower

required

for the Level 1 environmental assessment. It should

be noted that, although

these tests indicate

current thinking by OHEE, the final recommendations

may be significantly

expanded

or reduced.
10810.2

HEALTH

EFFECTS

BIOASSAYS Several test procedures

are currently

under consideration

for stream prioritization based on potential

health

effects;

these tests include

an acute toxicity

(in-vitro)

test, a mutagenic

screening

test, and a LD50 screening test.

Although

these tests do not provide

a directly

correlatable measure

of effects

on human health,

they are incorporated

to provide

an indication

of potential

adverse

effects,

to permit

semi-quantitative prioritization of samples,

and to direct

further

health

effects

studies. All health

effects

procedures

must be conducted

at EPA-approved

laboratories. 10.2.1 Acute Toxicity

(In-vitro)

Test An estimate

of the acute cellular

toxicity

of solids

can be obtained from an in-vitro

cell mortality

test utilizing

aveolar

macrophages

.from rabbit lungs.

The test consists

of incubating

the solid sample

in a culture medium for 24 hours,

adding

the macrophages

to the sample

and determining the number

of dead and living

cells after a second

incubation

period.

Cell mortality is determined

by means of a dye exclusion

technique,

i.e., living cells will not incorporate

the dye and are distinguishable

from the dead cells which will..This

test procedure

requires

approximately

0.5 grams of sample and 2 to 4 days for completion

of a limited

dose response

series. Present manpower

estimates

are in the range of I to 2 man-days

per series. 10.2.2 Mutagenicity

(Carcino•enicity) Screening

Test The mutagenic

screening

test is performed

according

to a modification of the procedure

developed

by Ames and co-workers

(Ref. 89, 90, 91), and is also used as a measure

of the potential

carcinogenicity

of a sample.

Three histidine deficient

Salmonella

typhimurim

strains

(TA-1535,

TA-1537,

and TA-1538) are Used; the reversion

of the strains

to prototrophy

indicates mutation. The three strains

have defective

DNA repair

systems

as well as defective lipopolysaccharide coats,

and exhibit

extreme

sensitivity

to observable mutational

events. The test consists

of dissolving

particulate

matter

samples

indimethylsulfoxide (DMSO),

followed

by exposure

of the bacterial

populations

to the dissolved particulate

material

on plates

using an agar overlay

method. Appropriate controls,

blanks,

and bacterial

toxicity

tests are included. The test procedure

requires

0.5 grams of sample

and 2 to 5 days for 109completion of a limited

dose response

series.

Estimated

manpower

requirements are approximately

2 man-days

per series. 10.2.3 LD50 Screening

Test The LDso test is used as a measure

of acute toxicity

in a whole animal. The test is performed

by administering

known levels

of the sample to a small population

of mice and extrapolating

the mortality

rate tO obtain an LDso value.

The test procedure

requires

14 days and 15 grams of sample. Manpower

requirements

are approximately

lman-d•y.

The information obtained can be supplemented

by performing

the mutagenic

screening

test described in Section

10.2.2

on urine samples

and detection

of toxicmetabolites produced

by the animal.

This would add approximately

1.2 man-days to the test cost. 10.3 ECOLOGICAL

EFFECTS

BIOASSAYS
A number

of test procedures

are currently

under consideration

for evaluating the effect

of samples

on aquatic

and terrestrial

forms of life. These p•ocedures

will utilize

selected

species

of animals

and plants

to provide an indicationof

the short term toxicity

of samples

to non-human forms of life.

In addition,

the tests can potentially

be extended

to

measure bioaccumulation

and entrance

into the food chain. 10.3.1 Aquatic

Effects Acute toxicity

tests are conducted

by exposing

selected

aquatic

species to several

levels

of pollutant

concentration

and determining

the mortality rate. Fathead

minnows

and daphnia

are widely

used in assessing

fresh water effects. Comparable

marine

organisms

are the sheephead

minnow

and mysid shrimp. All tests require

2 to 4 days for completion.

The fresh water tests require

about 1.2 man-days

and 40 liters

of sample.

The daphnia

and Shrimp require

approximately

3-4 man hours and 10 liters

of sample.

These tests can also be.expanded

to include

bioaccumulation

studies

by chemical tissue assay at an added cost of 6 man-days

per sample. 10.3.2 Terrestrial

Effects Although simple

general

tests for effects

on terrestrial

forms of life have not been as widely

developed

or applied

as aquatic

tests,

a few specifiC techniques are available.

The measurement

of ethylene

produced

by plantsexposed

to air pollutants

has been used

successfully

to assess

the health hazards of some pollutants.

This test requires

4 hours and takesapproximately:2 man-hours.

Measurement

of the 02 consumption

and CO 2 p.roduction of soil samples

containing

microorganisms

can also be used to assess

the impact of gaseous,

liquid

or solid samples.

Such tests require

600 hours for completion

and are inexpensive.

Finally,

exposure

of a microcosm

contai.ning a number

of terrestrial

species

(plants

and animals)

to samples

has been used in a few instances.

This test requires

20 days and manpower requirements range from 2 to 4 man-days

per system.

111REFERENCES

.7.

10.

Hamersma,

J. Wo, and Reynolds,

S. L., "Field Test Sampling/Analytical Strategies and Implementation

Cost Estimates;

Coal Gasification

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Research

Triangle

Park, N. C.,April

1976. Dorsey, J., C. Lockmuller,

L. Johnson,

and R. Statnick.

"Guidelines for Environmental

Assessment

Sampling

and Analysis

Programs

Level i•" U. S. Environmental

Protection

Agency,

Research

Triangle

Park, N. C. Mar 1976, 35 pp.

12. Hamersma,

J. W., and Reynolds,

S. L., "Tentative

Procedures

for Sampling and Analysis

of Coal Gasification

Processes,"

EPA Contract

No. 68-02-1412, Task Order No. 3, U. S. Environmental

Protection

Agency, Research Triangle

Park, N. C., Mar 1975, 150 pp. Brenchley, D. L., Turley,

D. C., and Yaime,

R. G., "Industrial

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Publishers,

Ann Arbor,

Mi., 1973, 439 pp. ASTM Committee

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Atmospheric

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1971 Annual Book of ASTM Standards,

Part 23, D1357-57,

American

Society for Testing

and Materials,

Philadelphia,

Pa., 1971, pp 291-297. C]ausen J., Grant,.

A., Moore,

D., and Reynolds,

S. L., "Field

Sampling for Cytotoxicity

Test Samples,"

EPA Contract

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Task Order Nos. 8, 14, 15, U. S. Environmental

Protection

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Research Triangle Park, N. C., Sept 1975, 87 pp. Bombaugh, K., Cavanaugh,

E., Dickerman,

J., Keil, S., Nelson,

T., Cowen, M., and Rosebrook,

D., "Sampling

and Analytical

Strategies

for Compounds in Petroleum

Refinery

Streams,"

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U. S. Environmental

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U. S. Federal

Power Commission, Docket

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County

of Los Angel.es,

Los Angeles, Ca., 1973, p 987. Shaw, H., and Magee,

E. M., "Evaluation

of Pollution

Control

in Fossil Fuel Conversion

Processes

in Gasification",

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Triangle

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D,3 a•d D'5• ITG••-•••;

Coal and Coke,"

1971 Annual Book of ASTM Standards,

Part 19, Dl145-53,

American

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and Materials,

Philadelphia,

Pa., 1971, pp 1208-1213. ASTM Committee

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Atmospheric

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1971 Annual Book of ASTM Standards,

Part 23, D1605-60,

American

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Philadelphia,

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14.
15.!6.
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18.

19.

ASTM Committee

D-3 and D-5, "Gaseous

Fuels;

Coil and Coke•"

1971 Annual Book of ASTMStandards,

Part 19, D1247-54,

American

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Philadelphia,

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Ist ed, AnnArborHumphrey Science

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Ann Arbor,

Mi,, 1970, p 150.
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Federal

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Washington,

D.C., 1972, p 480. Mueller, P.K., Chairman,

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in Air Pollution

and Industrial Hygiene Studies,"

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University

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Los Angeles, Ca., !971, p 170. American Conference

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Hygienists,

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Cincinnati,

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H., and Harris,

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meeting,

Denver,

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M., '!Particle

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T., Lambert,

J., and Zweig,

G., "Chemical Analysis of the Environment

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Ist ed, Plenum Press,

New York, •.Y., 1973, 384 pp. 22. Flegal,

C. A., Starkovich,

J. A., Maddalone,

R. F., Zee, C., and Kraft, M. L., "Procedures

for Process

Measurements,

Trace Inorganic

Materials," EPA Contract

No. 68-02-1393,

U. S. Environmental

Protection

Agency, Research Triangle

Park, N. C., July, 1975, 130 pp. 23. Geiver,

P. M., in "Air Pollution,"

Volume

II, A. C. Stern,

Ed., Academic Press, New York, N. Y., 1968, p 249. 24.

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W. E., "Some Theory

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1st ed, John Wiley and Sons, Inc., New York, N. Y., 1955, 500 pp. Maddalone, R. F., and Quinlivan,

S. C., "Technical

Manual

for Inorganic Sampling and Analysis,"

EPA Contract

No. 68-02-1412,

Task Order No. 16, U. S. Environmental

Protection

Agency,

Research

Triangle

Park, N. C., Apr 1976, Section

01-04. 26. ASTM Committee

D-19 and D-22, "Water;

Atmospheric

Analysis,"

1971 Annual Book of ASTM Standards,

Part 23, D2928-71,

American

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and Materials,

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Aerospace Materials, Sulfonates,

Petrolatum,

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and Materials,

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and Cellular

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Part 26, D2234'72,

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and Materials,

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J.W., and Mitchell,

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A., Williams,

E., and Wood, M., Anal. Chem. 3•9, 584 (1967). 53. Attari,

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1973. 54. Ahearn,

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60. Brown,

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in Geology," Elsevier

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Level I Organic

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on EPA Contract

No. 68-02-2150;

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Aerospace

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American

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for Testing

and Materials, Philadelphia, Pa,, 1971, pp 1072-1081. 76. Rao, C.N.R.,

"Chemical

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of Infrared

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London,

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1963, 683 pp.
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New York, N.Y., 1966, 560 pp.
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of Mass Spectrometry

to Organic

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New York, N•Y., 1966, 256 pp. 81. Budzikiewicz,

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Ca., 1976, 690 pp. 82. Imperial

Chemical

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Data Center,

Alder Maston,

Reading,

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Data,"

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Publishers,

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Analyst

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86. West• P.W., The Chemist

Analyst

35, 4 (1946).
87. Herdon,

G., "Small

Particle

Statistics,"

2nd ed, Academic

Press,

New York, N.Y., 1960, 520 pp. 88. Orr, C., and Dalla Valle,

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Measurement,

Size, Surface and Pore Volume,"

Ist ed, Macmillan

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ELG., Miller,

J.A. and Bartsch,

H., Proc.•Nat. Acad. Science

69:3Z28 90. Ames, B.W., Lee, F•D. and Durston,

W.E., Prec. Nat. Acad. Science

70: 782 (1973). 91. Ames, B.W., Durston,

W.E., Yamasaki,

E. and Lee, F.D., Prec. Nat. Acad. Science

70:2281

(1973). 117APPENDIX A DESIGN AND PREPARATION

OF A FIELD TESTING

UNIT (REFERENCES 1, 3, 6)
Mobile laboratories

in the form of vans or trailers

have been used very effectively

for a variety

of source

assessment

efforts

such as stack sampling,, ambient

air sampling

and water quality

measurements.

Because the use of a van as a mobile

laboratory

for on-site

analysis

is very desirable for the Level I effort,

this appendix

is included

to aid those contractors interested

in outfitting

their own vans. A.I ADVANTAGES In order to sample

a proposed

site in a timely

and efficient

manner, it is desirable

to fabricate

a field testing

unit which is completely

outfitted with all necessary

equipment

required

for Level I sampling

and on-site analysis.

In addition

to the obvious

advantages

Kith respect

to sampling, a major advantage

of such units lies in the fact that many samples may be or are unstable,

and delaying

the analysis

could result

in erroneous conclusions. In addition,

the results

for a given sample

are often quite unexpected and the presence

of an on-site

laboratory

allows

the immediate re-analysis of a check sample

and/or

modification

of the experimental

plan

on a real time basis,

which allows

the saving

of time, effort

and cost. In the phased

sampling

effort

for environmental

assessment,

many effluent parameters

must be determined

on-site

due to their unstable

nature. In addition,

the philosophical

aims of Level• 1 testing

in the phased approach can be enhanced

greatly

with an on-site

laboratory.

Awellequipped laboratory

will allow additional

Level I or "Semi-Level

2" samples to be taken so that the final Level 2 effort

can be focused

in greater detail, with a resultant

decrease

in cost for the Level 2 effort.

Finally, unanticipated problem

areas can be identified

in greater

detail

for the Level 2 effort. Most sampling

efforts

will require

the rental

of a van or trailer

to transport needed

equipment,

tools and reagents

from the laboratory

to the sampling source.

Driver

and mileage

rates must also be figured

into the overall cost.

Since the above costs are incurred

as a natural

outgrowth of most sampling

efforts,

the cost effectiveness

of a mobile

laboratory
118unit

is greatly

enhanced

since these normally

incurred

costs may be applied to the mobile

laboratory

unit.

An additional

advantage

is that sampling equipment

assembly,

sample

transfer

and equipment

clean-up

are facilitated by the additional

work space made available

in the mobile laboratory unit for all phases

and types of sampling

operations. A.2 COMPONENTS

AND LAYOUT This section

describes

the components

and layout

of a Level 1 sampling and on-site

analysis

room.

A van was chosen

as the room because

of the versatility and mobility

of the van compared

to a trailer,

particularly when many sites must be visited.

The discussion

below,

however,

also applies to the outfitting

of a trailer. Basic furnishings

of the Level I vans should

include:

• A refrigerator

for storing

ice and preserving

water samples.
An ice maker to provide

a continuous

and convenient supply of ice for cooling

down the SASS train i mpl ngers.Cabinets, drawers

and shelves

for storage

ofsampling equipment,

tools,

hardware,

spare parts,

glassware, sample

bottles,

reagents,

etc.

• Work surfaces

for assembling

equipment

andperforming analyses.

• Lockers

for storage

of rain gear, goggles,

overalls, etc.

• .A desk and 2,drawer

file for storage

of data, notebooks and instrument

and equipment

manuals. A laminar

flow bench for performing.operations such as sample

transfers

(particularly

those for trace analyses and toxicity

testing)

that are susceptible to ambient

contamination. Thework areas of the vans will be separated

into two general

areas: one for "clean"

operations

which will be away from the door and separated by curtains,

and one for "dirty"

operations.

A layout

design

for the furnishings listed

above is shown in Figure

31. Along with the basic floor plan, cutaway

views of the two side walls are. also presented.

119PARTfTION GASCHROMATOGRAPH

\GENERATOR •ARTITION CURTAIN

HOUSING CUTAWAY V IEW SHOW NG RI GHT S DE

R FT

WINDOW

WINDOW

WINDOW

LEFT SIDE

32 FTRIGHT SIDE DOOR

STORAGECABINET

ICE REFRIGERATOR MAKERTOP VIEW

GAS CHROMATOGRAPH, AND CARRIER AND CALIBRATION GASES

PARTfflON CURTAIN

CUTAWAY VIEW SHOWING LEFT SIDE

PARTITIONr/CURTAIN

Figure 31. Level 1 Multimedia

Mobile

Laboratory 120Several important

criteria

dealing

with functionality

and structural strength are incorporated

in the design

of the field test vans shown in Figure 31. These criteria

are: Functionality

• Maximize

work surfaces

and storage

spaCe.

• Separate

clean work areas from dirty work areas.

• Place related

supplies,

equipment

and work areas in close proximity. Structural Strength

and Safety

• Distribute

weight

evenly

from side to side.

• Place heaviest

load between

axles.

• Avoid installing

items that would require

bolts into housing

over a generator. Figure 31 shows an 8' x 32' van with a 15 KW generator

to supportthe basic van systems

such as air conditioning,

lights,

refrigerator,

ice maker, and gas chromatograph.

For a completely

independent

power supply

tosuPport all van and sampling

(SASS train)

systems,

a 30 KW towable.diesel generator is required•

Items shown in the: layout

are all flexible

in size and design

and can be chosen

and assembled

to make maximum

usage of the space inside

the vanL For example,

the work bench and storage

cabinet

at the rear of the van can be adjusted

to the same height

as the generator housing sheif to provide

a continuous,

level work surface

with wall cabinets providing additional

storage.

Good use can also be made of the areas over the wheel wells since certain

items can be built around.or

over the wells. Equipment for the Level 1 mobil•

test van is shown in Table 7. Additional equipment

which would be used for Level 2 source

assessments consists of high-accuracy,

continuous

monitors

for particulate

matter

and individual gases (i.e.• CO, NO x, SOx, 02, and C02); automatic,

compositing water samplers

with flow monitors;

high-accuracy

water analysis

instruments; and other special

capital

equipment

appropriate

for field use. This Level 2 sampling and analysis

equipment

can be carried

in the vans when space and

121Table 7. Level 1 Mobile

Van Equipment
Gas Sampling SASS Train Hi-Vol Ambient

Samplers Glass bulbs with a diaphragm

vacuum

pump for evacuation Gas AnalysisMultiple

column

and detector

gas chromatograph

for CO, SO x, N 2, CO 2, 02 C I C 6 hydrocarbons,

NH3, HCN, (CN)2 Water Sampling Portable Hach Sampling

Kit Positive displacement

pump and hoses Portable flow monitoring

devices Water Analysis Electrodes

and meters

to measure

pH, conductivity,

turbidity, and dissolved

oxygen Portable water analyzer

to perform

alkalinity,

hardness

and COD analysis Portable Hach Analysis

Kit weight capacities

permit.

The excess

can be drop-shipped

or placed

in a separate trailer

as appropriate.

However,

the cost, bulk and weight

of the equipment along with the infrequency

of its use make permanent

installation in the vans impractical.

122APPENDIX B

PROCESS DATA NEEDS

Table 8 delineates

the process

data needs for a phased

environmental .assessment. These needs are subcategorized

for plant characterization, plant operating

conditions,

plant stream

conditions,

and sampling/analysis.

123124125126APPENDIX C LIQUID CHROMATOGRAPHY

SEPARATION

PROCEDURE
Column: 200 mm x 10.5 mm ID, glass with teflon

stopcock. Adsorbent: Davison

Silica

Gel, 60-200

mesh, Grade 950, (Fisher

Scientific .Company). This adsorbent

is activated

at 110oc for two hours just prior to use. Cool in a desiccator. C.1 PROCEDURE

FOR COLUMN

PREPARATION Dry pack the chromatographic

column,

plugged

at one end.with

glass wool, with 6.0 grams,.of

freshly

activated

sili•a

gel. A portion

ofproperly activated

silica

gel weighing

6.0 ±0.2 g occupies

8 ml in a I•0 ml graduated cylinder.

Vibrate

the column

for a minute

to compact

the gel bed. Pour pentanei•tO

the solvent

reservoir

positioned

above the cO'l•mn and let the pentane

flow into the silica

gel bed until

the column

is homogeneous throughout

and free of any cracks

and trapped

ai• bubbles*. The total height

of the silica

bed in this packed

column

is 10 cm. The solvent void volume

of the column

is 2 to 4 ml. When the column

is fully prepared, allow the pentane

level in the column

•o drop to the top of the silica bed so that the sample

can be loaded

for subsequent

chromatographic elution.C.2 PREPARATION

OF THE SAMPLE At room temperature

evaporate

the solvent

from an aliquot

of solution containing at least 20 to 500 mg of sample.

The preferred

sample

weight

is lO0.mg. Weigh this sample

in a glass weighing

funnel.

In order tofacilitate transfer

of the sample,

add 0.5

to 1.0 g of activated

silica

gel to the sample

and carefully

mix this with the sample

using a micro-spatula.

A convenient

device

for the elimination

of gel bed cracks

and air bubbles is acetone

coolant,

which is subsequently

referred

to as the ACE B method. It consists

of a paper towel wound loosely

around

the glass column

along the region

of the crack or bubble;

the paper towel is periodically moistened with acetone.

The acetone

evaporation

cools the region

and dissipates the bubble

or crack.

127Table 9 shows the sequence

for the chromatographic

elution.

In order to ensure

adequate

resolution

and reproducibility, the column

elution rate is maintained

at I ml per minute. Table 9. Liquid

Chromatography

Elution

Sequence
No.

Volume Fraction Solvent

Composition Collected
I Pentane 25 ml10 ml10 ml 20% Methylene_.

chloride

in pentane

• •'wv(L50% Met•de in pentane Methylene chloride 10 ml 20% Methanol

in methylene

chlorid.;

• • 10 ml 50% Methanol

in •thylene

chloride

T•IO

ml

C.3 LOADING

SAMPLE

ON THE COLUMN Quantitatively transfer

the sample

into the Column

via the weighing funnel used for sample

preparation;

a micro-spatula

can be Used to aid in the sample

transfer.

Rinse the funnel*

with a few ml of pentane

tocomplete the quantitative

sample

transfer.

(Note:

Do not rinse with methylene chloride because

this solvent

will cause the aromatics

to elute width the paraffins.) Add the solvent

slowly

to minimize

disturbing

the gel bed and eliminate the trapped

air bubbles,

particularly

in the zone of thesamplecontaining silica

gel, by using the ACE B approach

(see footnote,

preceding page). The chromatographic

system

is now ready for sample

fractionation.

Save this weighing

funnel,

for subsequent

additional

rinsing

with the solvents used at interim

fractions

up to methylene

chloride. 128C.4

CHROMATOGRAPHIC

SEPARATION

INTO 8 FRACTIONS The volume

of solvents

shown in Table 9 represents

the solvent

volume collected for that fraction.

If the volume

of solvent

collected

is |ess than volume

actually

added due to evaporation,

add additional

solvent

as necessary. In all cases,

however,

the solvent

level in the column

should be at the top of the gel bed, i.e.,the

sample-containing zone, at the end of the col|ection

of any sample

fraction.. After the first fraction

is collected,

rinse the original

sample weighing funnel with a few ml of the Fraction

Number

2 solvent

(20% methylene chloride/pentane) and carefully

transfer

this rinsing

into the column.. Repeat

as necessary

for Fractions

3 and 4.

129APPENDIX D PREPARATION OF XAD-2 RESIN
The XAD-2 resin to be used in the SASS train sorbent

trap must be cleaned prior to use. The resin as obtained

from Rohm

and Haas is soaked with an aqueous

salt solution.

This salt solutionplus

residual

monomer and other trace organics

must be removed

before

the resin can be used for sampling trace organics. Transfer the resin to a large Soxhiet

extractor

with a 1.5-1iter dumping Volume.

This requires

2 to 2.5 liters

of solvent

in the 3-1iter supply flask.

The XAD-2 resin is then extracted

in sequence

with the following Solvents

and times:

• Water

22 hrs,

• Methanol

22 hrs;

• Anhydrous

ether

8 hrs,

o Pentane

22 hrs. The water removes

the salt solution

and any water soluble

organic material. Methanol

removes

the residual

water from the resin and ether

removes the majority

of the polar organic

material.

Pentane

is used as the final stage because

it is the solvent

used in the actual

extraction of Collected

material

from the resin. After the final pentane

extraction,

transfer

the XAD-2 resin

into a clean flask and dry it under a vacuum

for 18 hrs using mild heat

from a heat lamp.

130tt':CHNICAL REPORT

DATA
E pA-.600/2-76-160a
IERL-RTP

Procedures

Manual:

Level 1 Environmental Assessment

}. RECIPIENT'SACCESSIOP•ND.

$. REPORT DATE

TRW Systems

Group lOne Space Park Redondo Beach

California

90278 June 1976 PERFORMING ORGANIZATION

CODE AUTHOR{S) J.W. Hamersma,

S.L. Reynolds

• and

s. PERFORMING

ORGANIZATION

REPORT NO R.F. Maddalone 24916-6040-RU

00 10, PROGRAM

ELEMENT

NO. lAB013; ROAP

21AAZ-015 11. CONTRACT/GRANT

NO. 68-02-1412, Task 18 13: TYPE OF REPORT AND PERIOD COVERED _T_ask Final;

2-5/76 14. SPONSORING

AGENCY CODE EPA, Office

of Research

and Development Industrial Environmental

Research

Laboratory Research Triangle

Park,

NC 27711 EPA-ORD

•S. SUPPLEMENTARY

NOTES• IERL-RTP

project

officer

for this m,•mual

is R.M. Statnick, Mail Drop 62, (919) 549-8411,

Ext 2557.

,•. ASSTRAC•

The manual

gives Level 1 procedures

(recommended

by Industrial

Environ- mental Research

Laboratory--Research Triangle

Park) for personnel

experienced

in coIlecting and analyzing

samples

from industrial

and energy

producing

processes. The phased

environmental

assessment

strategy

provides

a framework

for determining industry, process,

and stream

priorities

on the basis of a staged

samplingand

analy- 3is technique.

(Level

1 is a screening

phase that characterizes

the pollutant

potential af process

influent

and effluent

streams.

) The manual

is divided

into two major !sections: sampling

procedures

and analytical

procedures.

The sampling

section

is further divided

into five chapters:

fugitive

emissions,

gases,

aerosols,

liquids (including slurries),

and solids.

The analytical

section

is divided

into three chapters: inorganic, organic,

and bioassays.

L DESCRIPTORS Pollution•ampling•nalyzing:Industrial Processes Energy ConversionBG.as Sampling lOassay
Unlimited KEY WORDS AND DOCUMENT

ANALYSIS

EPA Form 2220,1 (9-73) b. IDENTIFIERS/OPEN

ENDED TERMS Pollution Control Stationary Sources EnvironmentalAssessmentEnergy Processes Fugitive Emissions
19. SECURITY

CLASS Unclassified c. COSA]I |:icld/Gmup 13B 07D 14B llG

131 AerosolsLiquidsSlurriesSolidsInorganicCompoundsOrganic Compounds

20. SECURITY

(:LASS (l'hispage) Unclassified

21. NO. OF PAGES14513H10A, 10B 07B D6A 07C