v>EPA
United States Environmental Monitoring Systems EPA-600/4-84-076
Environmental Protection Labortory December 1984
Agency Las Vegas NV 89114
Research and Development
Of
Hazardous Waste
SitesA Methods
Manual:
Volume II. Available
Sampling Methods,
Second Edition
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EPA 600/4-84-076
December 1984
CHARACTERIZATION OF HAZARDOUS
WASTE SITES--A METHODS MANUAL
VOLUME I I
AVAILABLE SAMPLING METHODS
Second Edition
by
Patrick J. Ford
Paul J. Turina
Douglas E. Seely
GCA CORPORATION
GCA/TECHNOLOGY DIVISION
Bedford, Massachusetts 01730
Prepared for
Lockheed Engineering and Management
Services Company, Inc.
Las Vegas, Nevada 89109
Under
EPA Contract No. 68-03-3050
EPA Project Officer
Charles K. Fitzsimmons
Advanced Monitoring Systems Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89114
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89114
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NOTICE
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under contract number 68-03-3050
to Lockheed Engineering and Management Services Company, Inc. and subcontract
to GCA Corporation/Technology Division. It has been subject to the Agency's
peer and administrative review, and it has been approved for publication. The
contents reflect the views and pol icies of the Agency. Mention of trade names
or commercial products does not constitute endorsement or recommendation for
use.
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FOREWORD
Available Sampling Methods is part of a muItivoIume manual, entitled
Characterization of Hazardous Waste Sites--A Methods Manual, deveI oped by the
U.S. Environmental Protection Agency. The sampling methods-document is dedi-
cated to sampling procedures and sampling information only, and is meant to be
used in conjunction with two companion documents that address general site
characterization approaches, and available laboratory analytical methods for
sample analysis. The sampling volume describes a collection of methods and
materials sufficient to address most sampling situations that arise during
routine waste site and hazardous spill investigations. The methods are com-
piled with detailed, practical information to provide field investigators with
a set of functional operating procedures.
The first companion volume, Integrated Approach to Hazardous Waste Site
Characterization, includes discussions on preliminary assessment, initial data
evaluation, administrative procedures, offsite reconnaissance, site inspection,
chain of custody, quality assurance, safety and training in addition to con-
siderations concerning sampling strategy and methods selection. The second
companion document, Available Laboratory Analytical Methods, outlines detailed
methodology suitable for hazardous waste analysis and is organized by media and
compound.
111
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ABSTRACT
Investigations at hazardous waste sites and sites of chemical spills
often require onsite measurements and sampling activities to assess the type
and extent of contamination. This document is a compilation of sampling
methods and materials suitable to address most needs that arise during
routine waste site and hazardous spill investigations.
The sampling methods presented in this document are compiled by media,
and were selected on the basis of practicality, economics, representativeness,
comparability with analytical considerations, and safety, as well as other
criteria. In addition to sampling procedures, sample handling and shipping,
chain-of-custody procedures, instrument certification, equipment fabrication,
and equipment decontamination procedures are described.
Sampling methods for soil, sludges, sediments, and bulk materials cover
the solids medium. Ten methods are detailed for surface waters, groundwater
and containerized liquids; twelve are presented for ambient air, soil gases
and vapors, and headspace gases. A brief discussion of ionizing radiation survey
instruments is also provided.
IV
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CONTENTS
Sect i on Rev i s i on
1.0 Introduction
1 .1 General 1
1.2 Method Selection Criteria 1
1.3 Purpose and Objective of Sampling 1
1 .4 Types of Samp Ies 1
1.5 Samp I i ng PIan 1
1.6 Implementation of Sampling Plan 1
1 . 7 References 0
2.0 Solids
2.1 General 1
2.2 Soi Is 1
2.2.1 Method 11-1: Soil Sampling with a Spade
and Scoop 1
2.2.2 Method I I-2: Subsurface Solid Sampling
with Auger and Thin-Wall Tube Sampler 0
2.3 Sludges and Sediments 0
2.3.1 Method I I-3: Collection of Sludge or
Sediment Samples with a Scoop 0
2.3.2 Method I I-4: Sampling Sludge or Sediments
with a Hand Corer 0
2.3.3 Method I I-5: Sampling Bottom Sludges or
Sediments with a Gravity Corer 0
2.3.4 Method I I-6: Sampling Bottom Sludges or
Sediments with a Ponar Grab 0
2.4 Bulk Materials 0
2.4.1 Method I I-7: Sampling of Bulk Material
with a Scoop or Trier 0
2.4.2 Method I I-8: Samp I ing Bulk Materials with
a Grain Thief 0
2 . 5 References 0
3.0 Liquids
3.1 General 0
3.2 Surface Waters 0
3.2.1 Method I I 1-1: Sampling Surface Waters Using
a Dipper or Other Transfer Device 0
3.2.2 Method III-2: Use of Pond Sampler for the
Collection of Surface Water Samples 0
3.2.3 Method III-3: Peristaltic Pump for Sampling
Surface Water Bodies 0
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CONTENTS (continued)
Sect I on Rev IsI on
3.2.4 Method I I 1-4: Collection of Water Samples
from Depth with a Kemmerer Bottle 0
3.3 Containerized Liquids 0
3.3.1 Method III-5: Collection of Liquid
Containerized Wastes Using Glass Tubes 0
3.3.2 Method III-6: Sampling Containerized Wastes
Using the Composite Liquid Waste Sampler
(Col iwasa) 0
3.4 Groundwater 0
3.4.1 Method III-7: Purging with a Peristaltic Pump 0
3.4.2 Method III-8: Purging with a Gas Pressure
D i spIacement System 0
3.4.3 Method III-9: Sampling Monitor Wells with a
Bucket Type Bai ler 0
3.4.4 Method 111-10: Sampling Monitor Wells with a
Peristaltic Pump 0
3.4.5 Method 111-11: Sampling Monitor Wells with a
Submersible Pump 0
3 . 5 References 0
4.0 Gases, Vapors and Aerosols
4.1 General 0
4.2 Ambient °
4.2.1 Method IV-1: Determining Oxygen Content in
Ambient and Workplace Environments with a
Portable Oxygen Monitor 0
4.2.2 Method IV-2: Determination of Combustible Gas
Levels Using a Portable Combustible Gas
Indicator 0
4.2.3 Method IV-3: Monitoring Organic Vapors Using a
Portable Flame lonization Detector 0
4.2.4 Method IV-4: Monitoring Toxic Gases and Vapors
Using a Photoionization Detector 0
4.2.5 Method IV-5: Use of Portable, Field-Operable
Gas Chromatographs 0
4.2.6 Method IV-6: Stain Detector Tube Method for
Sampling Gaseous Compounds 0
4.2.7 Method IV-7: Sampling for Volatile Organics in
Ambient Air Using Solid Sorbents 0
4.2.8 Method IV-8: Collecting Semi volatile Organic
Compounds Using Polyurethane Foam 0
4.2.9 Method IV-9: Determination of Total Suspended
Particulate in Ambient Air Using High Volume
Samp I ing Technique 0
4.3 Soil Gases and Vapors
4.3.1 Method IV-10: Monitoring Gas and Vapors from
Test Hole 0
4.3.2 Method IV-11: Monitoring Gas and Vapors from
We I Is 0
vi
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CONTENTS (continued)
Sect I on Rev IsI on
4.4 Headspace Gases
4.4.1 Method IV-12: Sampling of Headspace Gases in
Sem i sea Ied VesseIs 0
4.4.2 Method IV-13: Sampling of Headspace Gases in
Sea Ied VesseIs 0
4. 5 References 0
5.0 Ionizing Radiation
5.1 General 0
5.2 Personnel Monitors 0
5.3 Survey Instruments 0
5.3.1 Method V-1 : Radiation Survey Instruments Q
6.0 Bibl iography 0
Appendices
A. Sample Containerization and Preservation 0
B. Equipment Availability and Fabrication 0
C. Packing, Marking, Labeling, and Shipping of Hazardous
Material Samples 0
D. Document ControI/Chain-of-Custody Procedures 0
E. Decontamination Procedures 0
F. Instrument Certification 0
G. Appl icable Tables 0
VI I
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FIGURES
Rev IsI on
1-1 Types of material 0
2-1 Augers and thin-wall tube sampler 0
2-2 Hand corer 0
2-3 Gravity corers 0
2-4 Ponar grab 0
2-5 Samp I ing trier 0
2-6 Grain thief 0
3-1 Pond sampler 0
3-2 Peristaltic pump for liquid sampling 0
3-3 Peristaltic pump for liquid sampling (modified) 0
3-4 Modified Kemmerer sampler 0
3-5 Composite liquid waste sampler (COLIWASA) 0
3-6 Sample drillers log 0
3-7 Gas pressure displacement system 0
3-8 Teflon bai ler 0
4-1 Calibration schematic for rotameter and needle valve
combination 0
4-2 Calibration configuration for constant flow samplers 0
4-3 Tenax sampler 0
4-4 PUF sampling train schematic 0
VI I I
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FIGURES (continued)
jmber Rev IsI on
4-5 Exploded view of typical high-volume air sampler parts 0
4-6 Assembled sampler and shelter 0
4-7 Bar hole-maker 0
4-8 Gas samp I ing we I I 0
4-9 Drilling mechanism 0
TABLES
Rev i s i on
4-1 Compounds Shown Amenable to Field GC Analysis 0
4-2 Selected Retention Times 8-inch 3 percent Diisodecyl
Phthalate on Chromasorb W 0
4-3 Selected Retention Times 8-inch 10 percent OV-101 on
Chromasorb W GC Column 0
4-4 Selected Retention Times 8-inch 1 percent TCEP on
Chromasorb W W-HP 0
4-5 Compounds Successfully Monitored Using Tenax Sampling
Protocols 0
4-6 Literature Summary - Volatile Organics Amenable to
Collection by Tenax Sorbent Cartridges 0
4-7 Approximate Retention Volumes at 38°C (100°F) 0
4-8 Organic Compounds Collected in Ambient Air Using Low
Volume or High Volume Polyurethane Foam Samplers 0
IX
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SECTION 1 .0
INTRODUCTION
1.1 GENERAL
Investigations at hazardous waste and environment-threatening spill sites
place more restrictive demands on personnel, materials and methodologies than
those usually found in routine environmental surveys. As a result, traditional
procedures and protocols used for the acquisition of environmental samples
often fail to meet the rigors and demands required for many hazardous waste
sampling applications. Thus, the collection of hazardous waste samples will
frequently require specialized equipment and protocols either developed
specifically for such uses or modified from preexisting materials and/or
techniques. Some important considerations are:
Versati I ity--Methods and materials must be suitable to a wide range
of situations and applications because of the unknown nature of many
hazardous waste investigations and environmental spill responses.
Safety--Hazardous wastes, by definition, are associated with both
acute and chronic exposure to dangerous, toxic chemicals and this
dictates that protective sample collection methods be used to
minimize personnel exposure. In addition, instrumentation and
equipment must be safe for use in the atmospheres in which they are
being operated.
Decontamination--Because of the nature of the materials being sampled,
the option of using disposable sampling equipment must be considered
since attempting field cleanup efforts may be impractical.
Ease of Operation--Hazardous waste site investigations and response
actions at environment-threatening spills generally require some
level of hazard protection that may be cumbersome, limit the field of
vision, or fatigue the sampler. Sample collection procedures
must therefore be relatively simple to follow, expedite sample
procurement and to reduce the chance of fatigue. Col lection and
monitoring equipment should be simple to operate, direct reading,
and should not be unwieldy.
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These and other factors associated with the procurement of hazardous waste
samples need to be addressed in a compilation of practical, cost effective,
and reliable methods and procedures capable of yielding representative samples
for a diverse number of potential parameters and chemical matrices. These
methods must be consonant with a variety of analytical considerations running
the gamut from gross compatibility analyses (pH, flammabi I ity, water reactivity,
etc.) to highly sophisticated techniques capable of resolution in the part per
bi I I ion (ppb) range.
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1.2 METHOD SELECTION CRITERIA
Major emphasis must be placed on the selection of sampling methods. Even
a limited literature survey will disclose the existence of a great number of
sampling methods, all of which have certain merits that warrant consideration.
Therefore, selection criteria were chosen on which to base decisions for in-
cluding the sampling methods found in this manual. The following is a listing,
not necessarily in order of relative importance, of these criteria.
PracticaI ity
The selected methods should stress the use of simple, pragmatic, proven
procedures capable of being used or easily adapted to a variety of situations.
Representat i veness
The essence of any sampling campaign is to collect samples that are
representative of the material or medium under consideration. The selected
methods, although strongly taking into consideration economics, simplicity,
practicality, and portability, must also be capable of delivering a best
practicable representation of the situation under investigation.
Economics
The costs of equipment, manpower and operational maintenance need to be
considered in relation to overall benefit. Instrument durability, disposable
equipment, cost of decontamination, and degree of precision and accuracy
actually required are also factors to be considered.
Simplicity or Ease of Operation
Because of the nature of the material to be sampled, the hazards
encountered during sampling, and the cumbersome safety equipment sometimes
required, the sampling procedures selected must be relatively easy to follow
and equipment simple to operate. Equipment should be portable, lightweight,
rugged and, if possible, direct reading.
Comparability with Analytical Considerations
The uncertainty of sample integrity as it relates to the analytical
techniques to be used should be reduced whenever possible. Errors induced by
poorly selected sampling techniques, especially those used in uncontrolled
situations, can be the weakest link in the quality of the generated data.
Special consideration must therefore be given to the selection of sampling
methods in relation to any adverse effects that, might surface during
analysis. Proper materials of construction, sample or species loss, and
chemical reactivity are some of the factors that must receive attention.
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Versati I itv
The diversity and sheer numbers of potential parameters and scenarios
often preclude the use of novel approaches that are designed or better suited
for classifying a small number of compounds in a limited, defined environment.
The methods in question must be adaptable to a variety of sampling situations
and chemical matrices. This factor should not, however, jeopardize sample
integrity.
The risk to sampling personnel, intrinsic safety of instrumentation, and
safety equipment required for conducting the sampling all need to be evaluated
in relation to the selection of proper methods and procedures.
The above criteria were consulted during the selection of each of the
methods listed in the following sections. Obviously, tradeoffs were necessary,
and therefore, some methods may prove excellent for some situations and less
satisfactory for others. This factor must be considered by any field
investigator before using the procedures outlined here.
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1.3 PURPOSE AND OBJECTIVE OF SAMPLING
The basic objective of any sampling compaign is to collect a sample which
is representative of the media under investigation. More specifically, the
purpose of sampling at hazardous waste sites is to acquire information that
will aid investigators in determining the presence and identity of onsite
contaminants and the extent to which these compounds have become integrated
into the surrounding environment. This information can then be used as
support for future litigations or as input to remedial investigations and risk
assessments.
The term "sample" has already been defined as a representative part of the
media under investigation. Representativeness, however, is a relative term and
must be carefully considered, along with several other criteria, prior to the
acquisition of samples. A I ist of the criteria is as follows.
Representativeness--This sample possesses the same qualities or
properties as the material under consideration. The degree of
resemblance of the sample to the material in question is determined
by the desired qualities under investigation and analytical techniques
used.
Sample sizeThis should be chosen carefully in respect to physical
properties of the entire object and the requirements and/or
limitations of both sampling and analytical techniques.
Number and/or the frequency of subsample--Decisions on these
considerations are based on what types of statistical information are
desired and the nature of the material collected.
Maintenance of sample integrity--The sample must retain the properties
of the original medium conditions (at the time of sampling) through
collection, transport, and delivery to the analyst.
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Section 1 .4
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1 .4 TYPES OF SAMPLES
Before defining the general sample types, the nature of the media or
materials under investigation must be discussed. Materials can be divided
into three basic groups as outlined in Figure 1-1.1
Of least concern to the sampler are homogeneous materials. These
materials are generally defined as having uniform composition throughout.
In this case, any sample increment can be considered representative of the
material. On the other hand, heterogeneous samples present problems to the
sampler because of changes in the quality of the material over distance.
When discussing types of samples, it is important to distinguish between
the type of media to be sampled and the sampling technique that yields a
specific type of sample. In relation to the media to be sampled, two basic
types of samples can be considered: the environmental sample and the hazardous
sample.
Environmental samples (ambient air, soils, rivers, streams, or biota) are
generally dilute (in terms of pollutant concentration) and usually do not
require the special handling procedures used for concentrated wastes. However,
in certain instances, environmental samples can contain elevated concentrations
of pollutants and in such cases would have to be handled as hazardous samples.
Hazardous or concentrated samples are those collected from drums, tanks,
lagoons, pits, waste piles, fresh spills, etc., and require special handling
procedures because of their potential toxicity or hazard. These samples can be
further subdivided based on their degree of hazard; however, care should be
taken when handling and shipping any wastes believed to be concentrated,
regardless of the degree.
In general, two basic types of sampling techniques are recognized, both of
which can be used for either environmental or concentrated samples.
Grab Samples
A grab sample is defined as a single sample representative of a specific
location at a given point in time. The sample is collected all at once and at
one particular point in the sample medium. The representativeness of such
samples is defined by the nature of the materials being sampled. In general,
as sources vary over time and distance, the representativeness of grab samples
wi I I decrease.
Composite Samples
Composites are combinations of more than one sample collected at various
sampling locations and/or different points in time. Analysis of composite
yields an average value and can, in certain instances, be used as an alternative
to analyzing a number of individual grab samples and calculating an average
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Material
I
Homogeneous
No change of quality
throughout the material
i
He terogeneous
I
r
Discrete
Change of quality
throughout the material
I
Continuous
Change of quality
throughout the material
Homogeneous
Discrete Changes
Continuous Changes
Well-mixed liquids
Well-mixed gases
Pure metals
Ore pellets
Tablets
Crystallized rocks
Suspensions
Fluids or gases with gradients
Mixture of reacting compounds
Granulated materials with granules
much smaller than sample size
Source: Reference 1.
Figure 1-1. Types of material.
~O TO CO
CD 05 05
CQ < o
05 (-1-
(/)
ho o
O Z!
O 3
-h ->
o -
GO -t*
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Sect i on 1.4
Rev i s i on 1
Page 3 of 3
value. It should be noted, however, that compositing can mask problems by
diluting isolated concentrations of some hazardous compounds below detection
I imits.
For sampling situations involving hazardous wastes, grab sampling
techniques are generally preferred because grab sampling minimizes the amount
of time sampling personnel must be in contact with the wastes, reduces risks
associated with compositing unknowns, and eliminates chemical changes that
might occur due to compositing. Compositing is still often used for environ-
mental samples and may be used for hazardous samples under certain conditions.
For example, compositing of hazardous waste is often performed (after compati-
bility tests have been completed) to determine an average value over a number
of different locations (groups of drums). This procedure provides data that
can be useful by providing an average concentration within a number of units,
can serve to keep analytical costs down and can provide information useful to
transporters and waste disposal operations.
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1 . 5 SAMPLING PLAN
Sect i on 1.5
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Before any sampling activities are begun, it is imperative that the
purpose and goals of a program and the equipment, methodologies, and logistics
to be used during the actual sampling be identified in the form of a work or
sampling plan. This plan is developed when it becomes evident that a field
investigation is necessary and should be initiated in conjunction with or
immediately following the preliminary assessments. This plan should be
concise, comprehensible and address the following items:
Review existing work or background;
Define goals and scope of work;
Organization of the field teams;
Statistical strategy;
Quality assurance/Quality control procedures;
Safety considerations; and
Decontamination procedures.
Please note that this I ist of sampling plan components is not all
inclusive. Additional elements may be inserted or altered depending on the
needs of the project. It should be understood that in emergency situations
personal judgement may have to be implemented. In any event, actions should be
dictated by plan to maintain logical and consistent order to the task.
(Additional details concerning the development of a Sampling Plan can be found
i n Vo I ume I , Sect i on 6.)
Reviewing Existing Work or Background Information
A synopsis of the site operational history as well as a review of
previous study conclusions and recommendations are necessary in order to
familiarize the field team members with the investigation.
In addition, this section should include regional or state maps locating
the investigation area as well as detailed maps and photos of the local site.
Of particular importance to the investigators is information pertaining to the
following points: (1) the composition and characteristics of the wastes, (2)
the adequate storage or destruction of wastes on the site, (3) the routes which
the wastes could migrate off site, and (4) the effects that would occur (or
might have occurred) through the discharge of waste.
Goals and Scope
A clear definition of the goals of the investigation and a detailed
explanation of the tasks and phases designed to provide the information
necessary to obtain the goals should be included.
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The goals may be a general characterization of the site or a determination
of offsite migration of contaminants or the collection of physical evidence for
enforcement proceedings. Generally it is a combination of these or other
potential goals which must be considered. Investigators must be aware that
short-sighted goal assignment may limit utility of data for future applications.
The scope of the investigation should be outlined as discrete phases and
tasks. The sequence and timeframe for each task should be delineated on a
project time table or time line with key decision points and options clearly
d i spIayed.
Efficient arrangement of tasks to minimize onsite time will lead to reduced
risks by reducing exposure times.
Organization of the Field Teams
Before sampling can commence, the following responsibilities must be
delegated into the following roles:
Project Team Leader-- is primarily an administrator when not
participating in the field investigation.
Field Team Leader--is responsible for the overall operation and safety
of the field team.
Site Safety Officer-- is primarily responsible for all safety procedures
and operations.
Command Post Supervisor--serves as a means of communication and never
enters the exclusive area except for emergencies.
Work Party--performs the onsite tasks necessary to fulfill the
obj ect i ves.
Please note, that in many hazardous waste projects, one person may fulfill many
roIes.
Stat i st i caI Strategy
Implementation of the proper statistical strategy depends upon two
essential points, the objectives or goals of the sampling plan and the amount
of information available on the parameter or parameters of interest, i.e.
time, spatial distribution, variability, etc. The following are among the
different sampling schemes that could be chosen.
Random Samp I ing--
Random sampling uses the theory of random chance probabilities to choose
representative sample locations. Random sampling is generally employed when
little information exists concerning the material, location, etc. It is most
effective when the population of available sampling locations is large enough
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to lend statistical validity to the random selection process. Since one of the
main difficulties with random sampling deals with achieving a truly random
sample, it is advisable to use a table of random numbers to eliminate or reduce
bias (Appendix G).
Systematic Sampling--
Systematic sampling involves the collection of samples at predetermined,
regular intervals. It is the most often employed sampling scheme; however,
care must be exercised to avoid bias. If, for example, there are periodic
variations in the material to be sampled such that the systematic plan becomes
partially phased with these variations, bias will result.
A systematic sampling plan is often the end result of an approach that was
begun as random due to the tendency of investigators to subdivide large sample
areas into smaller increments before randomizing.
Stratified Samp I ing--
Data and background information made available from the preliminary site
survey, prior investigations conducted on site, and/or experience with similar
situations can be useful in reducing the number of samples needed to attain a
specified precision. Stratified sampling essentially involves the division of
the sample population into groups based on knowledge of sample characteristics
at these divisions. The purpose of the approach is to increase the precision
of the estimates made by sampling. This objective should be met if the
divisions are "selected in such a manner that the units within each division
are more homogeneous than the total population."2The procedure used basically
involves handling each division in a simple random approach.
Judgment Samp ling--
A certain amount of judgment often enters into any sampling approach. In
fact, a biased approach is the one most often employed when the intent is to
document the presence of contamination (e.g., for enforcement purposes). Since
judgment approaches tend to allow investigator bias to influence decisions,
care must be exercised. Poor judgment can lead to poor quality data and
improper conclusions. If judgment sampling is employed, it is generally
advisable that enough samples be collected to lend credence to any conclusion
drawn about the area under investigation because it is very difficult to
actually measure sample accuracy. This is especially true for enforcement
samples where the analytical results indicate no apparent sign of contamination.
In such cases it is important to reduce the chance of committing a Type II
statistical error. In such cases the inability to measure sample accuracy
makes it difficult to rule out Type II errors (i.e., the I ikeI ihood that
contaminants are present at the site even if not found in the samples).
Hybrid Sampling Schemes--
In reality, most sampling schemes consist of a combination or hybrid of the
types previously described. For example, when selecting an appropriate plan
for sampling drums at a hazardous waste site, the drums might be initially
staged based on preliminary information concerning contents, program objectives,
etc. (judgment, stratified sampling), and then sampled randomly within the
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specified population groups (random sampling). Hybrid schemes are usually the
method of choice as they can allow for greater diversity without compromising
the objectives of the program.
For further details on this subject, please refer to Volume I, Section 6
of this series.
Quality Assurance/Quality Control
The adherence to a proper Quality Assurance--Qua I ity Control plan is
essential for a successful sampling effort. The two major concerns of a QA/QC
plan are quality assurance samples and document control (chain of custody).
Quality Assurance Samples--
Quality assurance samples must be collected at any time legal action is
anticipated. It is recommended that quality assurance samples be collected
in a I I samp I ing surveys in order to know the qua I ity of data collected. These
additional samples are essential to any quality control aspects of the project
and may also assist in reducing costs associated with resampling brought about
by container breakage, errors in the analytical procedure, and data confirma-
tion. The following is a I ist of the types of quality assurance samples
requi red.
Sample Blanks--Sample blanks are samples of deionized/disti I led water,
rinses of col lection devices or containers, sampling media (e.g.,
sorbent), etc. that are handled in the same manner as the sample and
subsequently analyzed to identify possible sources of contamination
during collection, preservation, handling, or transport.
Pup I icates--Dupl icates are essentially identical samples collected
at the same time, in the same way, and contained, preserved, and
transported in the same manner. These samples are often used to
verify the reproducibi I ity of the data.
Spl it Samples--Spl it samples are duplicate samples given to the
owner, operator, or person in charge for separate independent
analysis.
Spiked Samples--Spiked samples are duplicate samples that have a
known amount of a substance of interest added to them. These
samples are used to corroborate the accuracy of the analytical
technique and could be used as an indicator of sample quality
change during shipment to the laboratory.
Document ControI/Cha i n-of-Custody--
Strict adherence to document and data control procedures is essential from
the standpoint of good quality assurance/quality control and should be insti-
tuted as routine in any hazardous waste investigation. It becomes especially
important when collected data is used to support enforcement litigations. All
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collected information, data, calibration and maintenance records, samples, and
documents, must therefore be accounted for and retrievable at any time during
an investigation.
The purpose of document control is to ensure that all project documents
be accounted for when the project is complete. Types of documents considered
essential include maps, drawings, photographs, project work plans, quality
assurance plans, serialized logbooks, data sheets, coding forms, confidential
information, reports, etc.
Chain-of-custody procedures are necessary to document the sample
identity, handling and shipping procedures, and in general to identify and
assure the traceability of generated samples. Custody procedures trace the
sample from collection, through any custody transfers, and finally to the
analytical facility at which point internal laboratory procedures take over.
Chain-of-custody is also necessary to document measures taken to prevent and/or
detect tampering with samples, sampling equipment or the media to be sampled.
A detailed description of Document Control/Chain-of-Custody Procedures can be
found in Appendix D and in Volume I, Section 2.
Safety--
A more detailed discussion of safety considerations can be found in
VoIume I , Sect i on 3 and VoIume IV (pending release of Volume IV refer to
Interim Standard Operating Safety Guides, Revised September 1982). These
considerations should be carefully reviewed before engaging in any hazardous
waste sampling endeavors. It is important, however, that safety be generally
discussed at this time to provide a necessary reminder of the importance of
taking proper, well developed precautions when dealing with hazardous materials.
Decontamination Procedures
Decontamination procedures are designed to provide two primary safeguards.
Prevent the movement of contaminated materials into noncontaminated
areas.
Insure that samples collected during the investigation are not
exposed to additional contamination from onsite materials or
samp I ing equ ipment.
Proper decontamination is not only a health and safety concern but also an
analytical and sampling consideration. The Sampling Plan will detail proper
decontamination procedures to safeguard both the onsite personnel and the
sample integrity. Appendix E provides generalized decontamination guidelines
exerpted from Interim Standard Operating Safety Guides, September 1982, Office
of Emergency and Remedial Response.
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1.6 IMPLEMENTATION OF SAMPLING PLAN
It is the responsibility of the Field Team Leader to implement and obtain
the goals of the Sampling Plan. This involves overseeing and coordinating
five primary tasks:
Management of the sampling team(s),
Coordination with the analytical lab(s),
Coordination with additional subcontractor efforts,
Implementation of the Safety Plan or Coordination with the Safety
Officer, and
Implementation of the QA/QC Plan or Coordination with the Quality
Assurance Officer.
Small scale efforts often utilize the Field Team Leader (FTL) as the Safety
Officer and the Quality Assurance Officer. As the Sampling Plan increases in
complexity, it becomes essential that the FTL designate Safety and Quality
Assurance Officers in order to insure proper implementation. It then becomes
the task of the FTL to coordinate their activities. Each of the five primary
tasks are described below:
Management of the Sampling Team
The key task here is to insure that the goals of the sampling plan are
obtained. In addition to the selection and proper implementation of methods,
the FTL must continually adjust, and carefully document changes to the sampling
plan to accommodate situations which may arise. This may involve, for example,
relocating or adding sampling locations if the investigation uncovers new
sources or should adverse weather make some locations inaccessible.
Thorough and detailed documentation of all onsite activities is also a
critical responsibility. This includes records of all expenditures, manpower,
and equipment uses and any changes of scope. These records are particularly
important for Superfund investigation or any investigation where attempts will
be made to recover costs from responsible parties. This aspect of the FTL's
responsibilities is often overlooked or downplayed, but to do so is likely to
later result in tremendous problems in cost recovery.
Coordination with the Analytical Lab
The sampling plan also serves to integrate the responsibilities of
Sampling Teams and the analytical labs. It is critical that the sampling
activities are coordinated with the laboratory. The following points
illustrate the extent of this coordination and its importance to the project:
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Sampling schedules must be arranged with the laboratory manager to
insure that the samples can be processed within the specified
holding times.
Labels and labeling information should be discussed. This will aid
in the orderly transfer of field information to the proper laboratory
personnel and insure that each sample receives only the specified
analyses.
Shipping arrangements, if necessary, must be agreed to in advance.
Selection of a carrier, delivery times, and billing procedures must
be mutually acceptable.
Preservation requirements and equipment decontamination procedures
should be specified. This would include specific recommendations
reagents and cleaning solvents.
A field and a laboratory coordinator should be designated from both
groups to serve as points of communication. In most situations, the
laboratory will specify the number and type of Quality Assurance/
Quality Control samples. Should this decision be made by field
personnel, information regarding these samples must be transmitted to
the Laboratory's QA/QC director.
Failure to properly coordinate these activities can result in complete
data loss, or at a minimum a reduction in its quality and overall reliability.
Either of these outcomes translates into potentially significant waste of time
and money.
Coordination with Other Subcontractor Efforts
Many investigations require the services of a team of subcontractors.
These include Drilling Contractors, Geophysical Investigation Teams, Aerial
Photographic Contractors, and Trade Contractors (electricians, plumbers,
carpenters and fencing contractors). It is the FTL's responsibility to
coordinate their activities, insure adherence to the sampling plan, or
contractual requirements.
Here again, thorough recordkeeping and documentation is critical.
ImpIementat i on of the Safety PI an
The Safety Plan must be implemented prior to full scale mobilization of
onsite activities. This would include establishing decontamination stations,
command posts, first aid stations, etc. If the scope of the investigation is
large, the FTL should designate a Site Safety Officer to implement the safety
plan.
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Volume I, Section 3 discusses the basic aspects of a Safety Plan. Volume
IV will provide details on the preparation and provisions of safety plans,
however until release of this document, this information is contained in the
Interim Standard Operation Safety Guides, September 1982, U.S. EPA, OERR.
ImpIementat i on of the QA/QC Plan.
The QA/QC Plan must address all phases of the investigation including
field measurements, laboratory analysis, subcontractor activities,
documentation/recordkeeping and report preparation. As with the Safety Plan,
the complexity and time demands of this task increase with the overall project
complexity. Therefore on larger projects, the FTL may designate a QA/QC
officer.
The FTL must be familiar with the terms of the QA/QC Plan and insure
that they are implemented by all field and laboratory personnel. Of particular
concern to the FTL are document control and chain of custody procedures. As
stated earlier, and cannot be over emphasized, are the demands on the FTL for
documentation and recordkeeping, these tasks must also closely adhere to docu-
ment control procedures. Without these records and documented assurance of
their completeness and validity litigation and cost recovery efforts will be
severely handicapped.
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1 .7 REFERENCES
Kateman, G. and F. W. Pijpers. Quality Control in Analytical
Chemistry. John Wiley and Sons, New York, 1981.
Smith, R. and G. James. The Sampling of Bulk Materials. Analytica
Sciences Monographs, Volume 8. The Royal Society of Chemistry,
London, 1981.
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SECTION 2.0
SOLIDS
2.1 GENERAL
The sampling of solid or semi-so I id materials is complicated by the
structural properties of the material. For example, the presence of entrapped
gases and fluids is often an integral part of the substance and may be of
consequence in the analytical techniques for which the sample was collected.
It is necessary in most cases to collect a sample which does not alter this
balance. In addition, physical strength and density of the material demand
sampling devices of significant rigidity and strength. As a result a great
deal of disturbance will occur at the sample-sampler interface. These effects
can be reduced by careful sampling and by collecting aliquots with a high
volume to surface area ratio.
A solid does not necessarily have uniform characteristics with respect to
distance or depth. Those portions which form boundaries with the container,
define the edges of a pile, or contact the atmosphere do not necessarily
represent the material as a whole. Care must be exercised in order to prevent
aeration or significant changes in moisture content. Samples should be tightly
capped and protected from direct light.1
Most commercially available solids sampling devices are steel, brass or
plastic. In general, use of stainless steel is the most practical and several
manufacturers will fabricate their equipment with all stainless steel parts on
a special order basis. Another alternative is to have sampler contact surfaces
Teflon coated. This can be accomplished by either sending the device to a
commercial coater or by in-house application of spray-on Teflon coatings. Some
devices, especially those for soil sampling, have traditionally been chrome-
or nickel-plated steel. These should be particularly" avoided, or the plating
should be removed because scratches and flaking of the plating material can
drastically effect the results of trace element analysis. Plated or painted
surfaces, can be used in many cases if the outside coating is first removed by
using abrasives. Such practice can yield a significant cost savings over more
expensive materials, so long as the exposed material will affect the sample.
This section is divided into three subsections which address the sampling
of soils, sludge and sediments, and bulk materials.
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2.2 SOILS
Soil sampling is an important adjunct to groundwater monitoring.
Sampling of the soil horizons above the groundwater table can detect
contaminants before they have migrated into the water table, and can help
establish the amount of contamination sorbed on aquifer solids that have the
potential of contributing to the groundwater contamination.
Soil types can vary considerably on a hazardous waste site. These
variations, along with vegetation, can effect the rate of contaminant migration
through the soil. It is important, therefore, that a detailed record be
maintained during sampling operations, particularly of location, depth, and
such characteristics as grain size, color and odor, and/or readings obtained
on field monitoring equipment. Subsurface conditions are often stable on a
daily basis and may demonstrate only slight seasonal variation especially with
respect to temperature, available oxygen, and light penetration. Changes in
any of these conditions can radically alter the rate of chemical reactions or
the activity of associated microbiological community. As a result samples
should be kept at their at-depth temperature or lower, protected from direct
light, sealed tightly in glass bottles, and analyzed as soon as possible.
The physical properties of the soil, its grain size, cohesiveness,
associated moisture, and such factors as depth to bedrock and water table will
limit the depth from which samples can be collected and the method required to
collect them. Often this information on soil properties can be acquired from
published soil surveys obtainable through the U.S. Geological Survey (USGS) and
other government and farm agencies. A comprehensive listing of these offices
and currently available soil surveys is included in the "NEIC Manual for
Groundwater/Subsurface Investigations at Hazardous Waste Sites."2Most of the
methods employed for soi I samp I ing at hazardous waste sites are adaptations of
techniques long employed by foundation engineers and geologists. This section
presents those methods which can be employed with a minimum of special training,
equipment or cost. More detailed methods capable of sampling to greater depths
in more difficult soil conditions, or that can simultaneously install
groundwater monitor wells, usually require professional assistance. These
techniques are discussed more fully in the "Manual for Ground-water Sampling
Procedures."3
Collection of samples from near the soil surface can be accomplished with
tools such as spades, shovels, and scoops. With this type of readily
available equipment the soil cover can be removed to the required depth; then
a stainless steel scoop can be used to collect the sample. An undisturbed
samp I e can be co I I ected from th i s excavat i on by emp I oy i ng a th i n wa I I tube
sampler. This device is, as the name implies, a metal tube generally 2.5 to
7.5 cm in diameter and 30.5 to 61.0 cm long. The tube is forced into the
soil, then extracted. Friction will usually hold the sample material in the
tube during the extraction. The construction material is generally steel, and
some samplers can utilize plastic liners and interchangeable cutting tips. The
liners are useful for trace element sampling but are generally not suitable
for organic analysis due to the possibility that materials in the liner will
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Section 2.2
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leach out and become incorporated as part of the sample. The liner tubes can
further be capped off and used as sample containers for transport to the lab.
Interchangeable cutting tips facilitate smoother penetration with reduced
sample disturbance. They are available in various styles and construction
suitable for moist, dry, sandy or heavy-duty applications. The design of these
cutting tips will further aid in maintaining the sample in the tube during
sample extraction.
Augers are also very effective for soil sampling. Bucket type augers can
be used directly for soil sample collection or to advance a borehole to the
desired depth so then a thin wall tube can be employed.
Kits are available that include, in conjunction with the tube sampler and
cutting tips, an auger point and a series of extension rods. These kits allow
for hand auger ing a borehole. The auger can then be removed and a tube sampler
lowered and forced into the soil at the completion depth. Though kits are
available with sufficient tools to reach depths in excess of 7 meters, soil
structure, impenetrable rock, and water levels usually prevent reaching such
completion depths. Kits that include 1 meter of drill rod and the ability to
order additional extensions will in practice prove satisfactory. The need for
soil information at greater depths will normally require professional
assistance. Consideration should be given to supplementing this information
with groundwater monitoring since soil sampling can be conducted in conjunction
with we I I completion.
For those wishing a more in-depth discussion of soils and soil sampling,
refer to the Preparation of Sol I Samp I ing Protocol: Techniques and
Strategies, (EPA 600/4-83-020) by Dr. Benjamin J. Mason, prepared under con-
tract to the U.S. Environmental Protection Agency, Environmental Monitoring
Systems Laboratory--Las Vegas, August 1983. This report discusses in detail
the factors that influence the selection of a particular sampling scheme or
the use of a particular sampling method with a strong emphasis on statistical
design and data analysis. Another document, Soil Sampling Quality Assurance
User's Guide. (EPA 600/4-84-043) by Dr. Delbert S. Barth and Dr. Benjamin J.
Mason, prepared by the Environmental Research Center, University of Nevada-
Las Vegas under a cooperative agreement with the Environmental Protection
Agency (May 1984) will also be helpful.
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Section 2.2.1
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2.2.1 METHOD 11-1: SOIL SAMPLING WITH A SPADE AND SCOOP
Discussion
The simplest, most direct method of collecting soil samples for
subsequent analysis is with the use of a spade and scoop. A normal lawn or
garden spade can be utilized to remove the top cover of soil to the required
depth and then a smaller stainless steel scoop can be used to collect the
sample.
This method can be used in most soil types but is limited somewhat to
sampling the near surface. Samples from depths greater than 50 cm become
extremely labor intensive in most soil types. Very accurate, representative
samples can be collected with this procedure depending on the care and
precision demonstrated by the technician. The use of a flat, pointed mason
trowel to cut a block of the desired soil will be of aid when undisturbed
profiles are required. A stainless steel scoop or lab spoon will suffice in
most other applications. Care should be exercised to avoid the use of devices
plated with chrome or other materials. Plating is particularly common with
garden implements such as potting trowels.
Procedures for Use
1. Carefully remove the top layer of soil to the desired sample depth
with a precleaned spade.
2. Using a precleaned stainless steel scoop or trowel, remove and discard
a thin layer of soil from the area which comes in contact with the
shove I.
3. Transfer sample into an appropriate sample bottle with a stainless
steel lab spoon or equivalent.
4. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach supple-
mented by a minimal holding time. For specific containerization and
preservation requirements consult Appendix A.
5. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag" carefully and clearly", addressing all the categories or
parameters. Complete all chain-of-custody documents and record in
the field log book.
6. Decontaminate equipment after use and between sample locations. For
specific decontamination guidelines, consult Appendix E.
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Section 2.2.2
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2.2.2 METHOD I I-2: SUBSURFACE SOLID SAMPLING WITH AUGER
AND THIN-WALL TUBE SAMPLER
Discussion
This system consists of an auger bit, a series of drill rods, a "T"
handle, and a thin-wall tube corer (see Figure 2-1). The auger bit is used to
bore a hole to the desired sampling depth and then withdrawn. The auger tip
is then replaced with the tube corer, lowered down the borehole, and forced
into the soil at the completion depth. The corer is then withdrawn and the
samp Ie coI Iected.
Alternately the sample can be recovered directly from the auger. This
technique however, does not provide an "undisturbed" sample as would be
collected with a thin tube sampler. In situations where the soil is rocky, it
may not be possible to force a thin tube sampler through the soil or sample
recovery may be poor. Sampling directly from the auger may be the only viable
method. Several auger types are available which include Bucket type, continues
flight (screw) and posthole augers. Bucket types are good for direct sample
recovery and are fast and provide a large volume of sample. When continuous
flight (screw) augers are utilized, the sample can be collected directly off
the flights, however, this technique will provide a somewhat unrepresentative
sample as the exact sample depth will not be known. The continuous flights
auger are, however, satisfactory for use when a composite of the entire soil
column is desired. Posthole augers have limited utility for sample acquisition
as they are designed more for their ability to cut through fibrous, heavily
rooted, swampy areas. In soils where the borehole will not remain open when
the tool is removed, a temporary casing can be used until the desired sampling
depth is reached.
Uses
This system can be used in a wide variety of soil conditions. It can be
used to sample both from the surface, by simply driving the corer without
preliminary boring, or to depths in excess of 6 meters. The presence of rock
layers and the collapse of the borehole, however, usually prohibit sampling at
depths in excess of 2 meters. Interchangeable cutting tips on the corer reduce
the disturbance to the soil during sampling and aid in maintaining the core in
the device during removal from the borehole.
Procedures for Use
1, Attach the auger bit to a drill rod extension and further attach the
"T" handle to the drill rod.
2, Clear the area to be sampled of any surface debris (twigs, rocks,
litter). It may be advisable to remove the first 8 to 5 cm of
surface soil for an area approximately 15 cm in radius around the
dri I I ing location.
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Section 2.2.2
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r\
Figure 2-1. Augers and thin-wall tube sampler.
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Section 2.2.3
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3, Begin drilling, periodically removing accumulated soils. This
prevents accidentally brushing loose material back down the borehole
when removing the auger or adding drill rods.
4, After reaching desired depth, slowly and carefully remove auger from
boring. (Note: When sampling directly from auger, collect sample
after auger is removed from boring and proceed to Step 10.)
5, Remove auger tip from drill rods and replace with a precleaned
thin-wall tube sampler. Install proper cutting tip.
6, Carefully lower corer down borehole. Gradually force corer into
soil. Care should be taken to avoid scraping the borehole sides.
Hammering of the drill rods to facilitate coring should be avoided as
the vibrations may cause the boring walls to collapse.
7, Remove corer and unscrew drill rods.
8. Remove cutting tip and remove core from device.
9. Discard top of core (approximately 2.5 cm), which represents any
material collected by the corer before penetration of the layer in
question. Place remaining core into sample container.
10. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time. Consult Appendix A for
containerization and preservation recommendations.
11. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories or
parameters. Complete all chain-of-custody documents and record in
the field logbook.
12. Decontaminate sampling equipment after use and between sampling
locations. Refer to Appendix E for decontamination requirements.
Sources
deVera, E. R., Simmons, B. P., Stephens, R. D., and Storm, D. L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA 600/2-80-018,
January 1980.
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2.3 SLUDGES AND SEDIMENTS
In general and for the purpose of this manual, sludges will be defined as
semi-dry materials ranging from dewatered solids to high viscosity liquids.
Sediments are the deposited material underlying a body of water. On occasion
they are exposed by evaporation, stream rerouting, or other means of water
loss. In these instances they can be readily collected by soil or sludge
coI Iect i on methods.
Sludges can often be sampled by the use of a stainless steel scoop or
trier. Frequently sludges form as a result of settling of the higher density
components of a liquid. In this instance the sludge may still have a liquid
layer above it. When the liquid layer is sufficiently shallow, the sludge may
be scooped up by a device such as the pond sampler described in Section III,
Method III-2, or preferably by using a thin-tube sampler as described in this
section (see Method I I-4). The latter is preferable as it results in less
sample disturbance and will also collect an aliquot of the overlying liquid,
thus preventing drying or excessive sample oxidation before analysis. Sludges
which develop in 55-gallon drums can usually be collected by employing the
glass tubes used for the liquid portion sample (Method III-5) as a thin-tube
sampler. The frictional forces which hold the sludge in the tube can be
supplemented by maintaining a seal above the tube. When the overlying layer is
deep, a small gravity corer such as those used in I imno logical studies will be
useful. Gravity corers, such as Phlegers, are easier to preclean and
decontaminate than piston type corers.
If the sludge layer is shallow, less than 30 centimeters, corer
penetration may damage the container liner or bottom. In this instance a Ponar
or Eckman grab may be applicable, as grab samplers are generally capable of
only a few centimeters of penetration. Of the two, Ponar grab samplers are
more applicable to a wider range of sediments and sludges. They penetrate
deeper and seal better than the spring-activated Eckman dredges, especially in
granular substrates.
In many instances sediments and sludges can be collected with a
peristaltic pump as described in Method III-3. This method is limited to
slurried samples less than approximately 20 percent solid. The weight of the
material wi I I also greatly reduce the I ift capacity of the pump, however, it
may sti I I be useful in extending the reach of the sampler laterally toward the
center of a vessel. In slurries not fully agitated, a bias may also be
introduced toward the liquid portion of the material.
Sediments can be collected in much the same manner as described above for
sludges; however, a number of additional factors may be considered. Streams,
lakes, and impoundments, for instance, will likely demonstrate significant
variations in sediment composition with respect to distance from inflows,
discharges, or other disturbances. It is important, therefore, to document
exact sampling location by means of triangulation with stable references on
the banks of the stream or lake. In addition, the presence of rocks, debris,
and organic material may complicate sampling and preclude the use of or require
modification to some devices. Sampling of sediments should therefore be
conducted to reflect these and other variants.
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Section2.3.1
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2.3.1 METHOD II-3: COLLECTION OF SLUDGE OR SEDIMENT SAMPLES WITH A SCOOP
Discussion
Sludge and sediment samples are collected using the simple laboratory
scoop or garden type trowel specified in Method 11-1. This method is more
applicable to sludges but it can be used for sediments provided the water
depth is very shallow (a few centimeters). It should be noted, however,
that this method can be disruptive to the water/sediment interface and might
cause substantial alterations in sample integrity if extreme care is not
exercised. The stainless steel laboratory scoop is generally recommended due
to its noncorrosive nature. Single grab samples may be collected or, if the
area in question is large, it can be divided into grids and multiple samples
can be collected and composite.
Uses
This method provides for a simple, quick, and easy means of collecting a
disturbed sample of a sludge or sediment.
Procedures for Use
1, Sketch the sample area or note recognizable features for future
reference.
2, Insert scoop or trowel into material and remove sample. In the case
of sludges exposed to air, it may be desirable to remove the first
1-2 cm of material prior to collecting sample.
3, If compositing a series of grab samples, use a stainless steel mixing
bowl or Teflon tray for mixing.
4, Transfer sample into an appropriate sample bottle with a stainless
steel lab spoon or equivalent.
5, Check that a Teflon liner is present in cap if required. Secure the
cap tightly. The chemical preservation of-so I ids-is generally not
recommended. Refrigeration is usually the best approach supplemented
by a minimal holding time. Containerization and preservation
requirements are detailed in Appendix A.
6, Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record in
the field logbook.
7. Decontaminate sampling equipment after use and between sample
locations according to the guidelines presented in Appendix E.
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Section 2.3.2
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2.3.2 METHOD II-4: SAMPLING SLUDGE OR SEDIMENTS WITH A HAND CORER
Discussion
This device is essentially the same type of thin-wall corer described for
collecting soil samples (Method I I-2). It is modified by the addition of a
handle to facilitate driving the corer (see Figure 2-2) and a check valve on
top to prevent washout during retrieval through an overlying water layer.
Uses
Hand corers are applicable to the same situations and materials as the
scoop described in Method I I-3. It has the advantage of collecting an
undisturbed sample which can profile any stratification in the sample as a
result of changes in the deposition.
Some hand corers can be fitted with extension handles which will allow
the collection of samples underlying a shallow layer of liquid. Most corers
can also be adapted to hold liners generally available in brass, polycarbonate
plastic or Teflon. Care should be taken to choose a material which will not
compromise the intended analytical procedures.
Procedures for Use
1. Inspect the corer for proper preclean ing, and select sample location.
2, Force corer in with smooth continuous motion.
3, Twist corer then withdraw in a single smooth motion.
4, Remove nosepiece and withdraw sample into a stainless steel or
Teflon tray.
5, Transfer sample into an appropriate sample bottle with a stainless
steel lab spoon or equivalent.
6, Check that a Teflon liner is present in cap if required. Secure the
cap tightly. The chemical preservation of solids is generally not
recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time. Appendix A, Sample
Containerization and Preservation should be consulted for specific
requ i rements.
7, Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Complete all chain-of-custody documents and record
in the field logbook.
8. Decontaminate sampling equipment after use and between sample
locations as required by procedures in Appendix E, Decontamination.
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Section 2.3.2
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CHECK VALVE
(OPTIONAL)
.CORE CATCHER
(OPTIONAL)
NOSEPIECE
Figure 2-2. Hand corer.
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2.3.3 METHOD II-5: SAMPLING BOTTOM SLUDGES OR SEDIMENTS WITH A GRAVITY CORER
Discussion
A gravity corer is a metal tube with a replacement tapered nosepiece on
the bottom and a balI or other type of check valve on the top. The check
valve allows water to pass through the corer on descent but prevents a washout
during recovery. The tapered nosepiece facilitates cutting and reduces core
disturbance during penetration.
Most corers are constructed of brass or steel and many can accept plastic
liners and additional weights (see Figure 2-3).
Uses
Corers are capable of collecting samples of most sludges and sediments.
They collect essentially undisturbed samples which represent the profile of
strata which may develop in sediments and sludges during variations in the
deposition process. Depending on the density of the substrate and the weight
of the corer, penetration to depths of 75 cm (30 inches) can be attained.
Care should be exercised when using gravity corers in vessels or lagoons
that have liners because penetration depths could exceed that of the substrate
and result in damage to the liner material.
Procedures for Use
1. Attach a precleaned corer to the required length of sample line.
Solid braided 5 mm (3/16 inch) nylon line is sufficient; 20 mm (3/4
inch) nylon, however, is easier to grasp during hand hoisting.
2, Secure the free end of the line to a fixed support to prevent
accidental loss of the corer.
3, Allow corer to free fall through liquid to bottom.
4, Retrieve corer with a smooth, continuous lifting motion. Do not
bump corer as this may result in some sample loss.
5, Remove nosepiece from corer and slide sample out of corer into
stainless steel or Teflon pan.
6. Transfer sample into appropriate sample bottle with a stainless steel
lab spoon or equivalent.
7, Check that a Teflon liner is present in cap if required. Secure the
cap tightly. The chemical preservation of solids is generally not
recommended. Refrigeration is usually the best approach supplemented
by a minimal holding time. Refer to Appendix A for sample
containerization and preservation guidelines.
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Sect i on 2.3.3
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STAB I LIZING
FINS
CORE
CATCHER
NOSE PIECE
Figure 2-3. Gravity corers.
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Sources
Section 2.3.3
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Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories or
parameters. 'Complete all chain-of-custody documents and record in
the field logbook.
Consult Appendix E for decontamination requirements and decontaminate
sampling equipment after use and between sampling locations.
American Public Health Association. "Standard Methods for the
Examination of Water and Wastewater" 14th Edition, Washington, D.C.
1975.
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2.3.4 METHOD II-6: SAMPLING BOTTOM SLUDGES OR SEDIMENTS WITH A PONAR GRAB
Discussion
The Ponar grab is a clamshell type scoop activated by a counter lever
system. The shell is opened and latched in place and slowly lowered to the
bottom. When tension is released on the lowering cable the latch releases
and the lifting action of the cable on the lever system closes the clamshell
(see Figure 2-4).
Uses
Ponars are capable of sampling most types of sludges and sediments from
silts to granular materials. They are available in a "Petite" version with a
232 square centimeter sample area that is light enough to be operated without a
winch or crane. Penetration depths will usually not exceed several centimeters.
Grab samplers, unlike the corers described in Method II-5, are not capable of
collecting undisturbed samples. As a result, material in the first centimeter
of sludge cannot be separated from that at lower depths. The sampling action
of these devices causes agitation currents which may temporarily resuspend some
settled solids. This disturbance can be minimized by slowly lowering the
sampler the last half meter and allowing a very slow contact with the bottom.
It is advisable, however, to only collect sludge or sediment samples after all
overlying water samples have been obtained.
Procedures for Use
1, Attach a precleaned Ponar to the necessary length of sample line.
Solid braided 5 mm (3/16 inch) nylon line is usually of sufficient
strength; however, 20 mm (3/4 inch) or greater nylon line allows for
easier hand hoisting.
2, Measure and mark the distance to bottom on the sample line. A
secondary mark, 1 meter shallower, will indicate proximity so that
lowering rate can be reduced, thus preventing unnecessary bottom
d isturbance.
3, Open sampler jaws until latched. From this point on, support sampler
by its lift line or the sampler will be tripped and the jaws will
close.
4. Tie free end of sample line to fixed support to prevent accidental
loss of sampler.
5, Begin lowering the sampler until the proximity mark is reached.
6, Slow rate of descent through last meter until contact is felt.
7. Allow sample line to slack several centimeters. In strong currents
more slack may be necessary to release mechanism.
2-I5
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Section 2.3.4
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Page 2 of 3
Figure 2-4. Ponar grab
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Section 2.3.4
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Slowly raise dredge clear of water surface.
9. Place Ponar into a stainless steel or Teflon tray and open. Lift
Ponar clear of the tray.
10. Collect a suitable aliquot with a stainless steel lab spoon or
equivalent and place sample into appropriate sample bottle. Appendix
A contains containerization and preservation requirements.
11. Check for a Teflon liner in cap if required and secure cap tightly.
The chemical preservation of solids is generally not recommended.
Refrigeration is usually the best approach supplemented by a minimal
holding time.
12. Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories or
parameters. Complete all chain-of-custody documents and record in
the field logbook.
13. Consult Appendix E, Decontamination for appropriate decontamination
procedures to be used on sampling equipment after use and between
samp I ing locations.
Sources
American Public Health Association. "Standard Methods for the Examination
of Water and Wastewater" 14th Edition, American Public Health Association,
Washington, D.C. 1975.
Lind, Owen T. "Handbook of Common Methods in Limnology." C.V. Mosby
Company, St. Louis, 1974.
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Sect i on 2.4
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2.4 BULK MATERIALS
Unlike soils which are heterogeneous associations of earthen and
manufactured substances, bulk materials are generally a homogeneous collection
of a single identifiable product. They are usually contained in bags, drums
or hoppers although on occasion large amounts of the material may be piled
directly on the ground, either deliberately or as the result of a spill.
Those surfaces exposed to the atmosphere may undergo some chemical
alteration or degradation and should be avoided during sample collection.
Since the process producing the bulk material may demonstrate some variation
with respect to time, it is advisable to collect a series of samples as one
composite to represent the material.
Bulk materials in an unconsol idated state may be readily collected by a
stainless steel scoop. When the amount of the material is large, a composite
can be collected by the use of a grain thief (see Figure 2-6). This device is
essentially a long hollow tube with evenly spaced openings along its length.
This tube is placed inside an outer sleeve with similar openings and forced
into the material. The inner sleeve is rotated until its openings align with
those on the outer sleeve, thus allowing the material to enter. The inner
sleeve is then further rotated sealing the openings, the device is withdrawn,
and the sample recovered.
Grain thiefs are available in many materials including brass and various
plastics. As with other sampling devices, care should be taken to choose a
construction material which will not compromise the desired analytical results.
A more detailed treatment of this subject (Bulk Materials) can be found in
The Sampling of Bulk Materials by R. Smith and G. V. James, The Royal Society
of Chemistry, London (1981). Although this book does not deal specifically
with hazardous waste sampling, the concepts discussed, especially on the
subject of the establishment of a sampling scheme, are readily applicable.
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Section 2.4.1
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2.4.1 METHOD II-7: SAMPLING OF BULK MATERIAL WITH A SCOOP OR TRIER
Discussion
A typical sampling trier (Figure 2-5) is a long tube with a slot that
extends almost its entire length. The tip and edges of the tube slot are
sharpened to allow the trier to cut a core of the material to be sampled when
rotated after insertion into the material. Sampling triers are usually made
of stainless steel with wooden handles They are about 61 to 100 cm long and
1.27 to 2.54 cm in diameter. They can be purchased readily from laboratory
supply houses.
A laboratory scoop or garden variety trowel can also be used to sample
bulk material. The trowel looks I ike a small shovel. The blade is usually
about 7 by 13 cm with a sharp tip. A laboratory scoop is similar to the trowel,
but the blade is usually more curved and has a closed upper end to permit the
containment of material. Scoops come in different sizes and shapes. Stainless
steel or polypropylene scoops with 7 by 15 cm blades are preferred. A trowel
can be bought from hardware stores; the scoop can be bought from laboratory
supply houses.
Uses
The use of the trier is similar to that of the grain sampler discussed in
Method I I-8. It is preferred over the grain sampler when the powdered or
granular material to be sampled is moist or sticky.
The trowel or lab scoop can be used in some cases for sampling dry,
granular or powdered material in bins or other shallow containers. The lab
scoop is a superior choice since it is usually made of materials less subject
to corrosion or chemical reactions.
Procedures for Use
1. Insert the precleaned trier into the waste material at a 0 to 45°
angle from horizontal. This orientation minimizes the spillage of
sample from the sampler. Extraction of samples might require tilting
of the containers.
2, Rotate the trier once or twice to cut a core of material.
3, Slowly withdraw the trier, making sure that the slot is facing
upward.
4. Transfer the sample into a suitable container with the aid of a
spatula and/or brush.
5, If composite sampling is desired, repeat the sampling at different
points two or more times and combine the samples in the same sample
container.
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Section 2.4.1
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61-100 era,
(24-40")
\
f i
I-
1.27-2.54 en (%-!")
Source: Reference 4.
Figure 2-5. Sampling trier.
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Section 2.4.1
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6, Check that a Teflon liner is present in the cap if required. Secure
the cap tightly. The chemical preservation of solids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time. Consult Appendix A for
sample containerization and preservation requirements.
7, Label the sample bottle with the appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories or
parameters. Complete all chain-of-custody documents and record in
the field logbook.
8. Clean and decontaminate sampler after use and between sampling
locations as per guidelines presented in Appendix E, Decontamination.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA-600/2-80-018.
January 1980.
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2.4.2 METHOD II-8: SAMPLING BULK MATERIALS WITH A GRAIN THIEF
Discussion
The grain thief (Figure 2-6) consists of two slotted telescoping tubes,
usually made of brass or stainless steel. The outer tube has a conical,
pointed tip on one end that permits the sampler to penetrate the material
being sampled. The sampler is opened and closed by rotating the inner tube.
Grain thiefs are generally 61 to 100 cm long by 1.27 to 2.54 cm in diameter,
and they are commercially available at laboratory supply houses.
Uses
The grain thief is used for sampling powdered or granular wastes or
materials in bags, fiberdrums, sacks or similar containers. This sampler is
most useful when the solids are no greater than 0.6 cm in diameter.
Procedures for Use
1. While the precleaned sampler is in the closed position, insert it
into the granular or powdered material or waste being sampled from a
point near a top edge or corner, through the center, and to a point
diagonally opposite the point of entry.
2, Rotate the inner tube of the sampler into the open position.
3, Wiggle the sampler a few times to allow materials to enter the open
sIots.
4. Place the sampler in the closed position and withdraw from the
material being sampled.
5, Place the sampler in a horizontal position with the slots facing
upward.
6, Rotate and slide away the outer tube from the inner tube.
7, Transfer the collected sample in the inner tube into a suitable
sample container.
8. If composite sampling is desired, collect two or more core samples at
different points, and combine the samples in the same container.
9, Check that the Teflon liner is present in the cap if required. Secure
the cap tightly. THe chemical preservation of sol ids is generally
not recommended. Refrigeration is usually the best approach
supplemented by a minimal holding time. Appendix A should be
consulted for containerization and preservation requirements.
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Section 2.4.2
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Page 2 of 3
61-100 cm,
(24-40")
-HK-
1.27-2.54 en (%-!")
Source: Reference 4.
Figure 2-6. Grain thief.
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Section 2.4.2
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Page 3 of 3
10. Label the sample bottle with the appropriate sample tag. Be sure
to label the tag carefully and clearly, addressing all the
categories or parameters. Complete all chain-of-custody documents
and record in the field logbook.
11. Decontaminate equipment after use and between sampling locations
using recommended techniques of Appendix E.
Sources
deVera, E.R., Simmons, B.P., Stephens, R.D., and Storm, D.L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA-600/2-80-018.
January 1980.
Horwitz, W., Sense I, A., Reynolds, H., and Parks, D.L., editors. Animal
Feed: Sampling Procedure. In: Official Methods of Analysis. The
Association of Official Analytical Chemists. 12th Edition. Washington,
D.C. 1979.
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Section 2.5
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2.5 REFERENCES
1. Smith, R. and G. James. The Sampling of Bulk Materials. Analytical
Sciences Monograph, Volume 8. The Royal Society of Chemistry,
London. 1981.
2, Sisk, S. W. NEIC Manual for Groundwater/Subsurface Investigations
at Hazardous Waste Sites. EPA-330/9-81-002. 1981.
3, Sea If, M., J. McNabb, W. Dun lap, R. Crosby, and J. Fryberger.
Manual for Groundwater Sampling Procedures. R. S. Kerr Environmental
Research Laboratory, Office of Research and Development, Ada, OK.
1980.
4. deVera, E. R., B. P. Simmons, R. D. Stephen, and D. L. Storm.
Samplers and Sampling Procedures for Hazardous Waste Streams.
EPA-600/2-80-018. January 1980.
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Sect i on 3.1
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SECTION 3.0
LIQUIDS
3.1 GENERAL
Liquids by their nature are a relatively easy substance to collect.
Obtaining representative samples, however, is more difficult. Density,
volubility, temperature, currents, and a wealth of other mechanisms cause
changes in the composition of a liquid with respect to both time and distance.
Accurate sampling must be responsive to these dynamics and reflect their
actions.
For the purpose of this manual liquids will include both aqueous and
nonaqueous solutions and will be subdivided as surface waters, containerized
liquids, and ground waters. Surface waters will be considered as any fluid
body, flowing or otherwise, whose surface is open to the atmosphere. This
will include rivers, streams, discharges, ponds, and impoundments, both
aqueous and nonaqueous. The containerized liquid section will address
sampling of both sealed and unsealed containers of sizes varying from drums to
large tanks. Some overlap may occur between these two sections; when in doubt,
both sections should be consulted. The groundwater section will be concerned
with obtaining samples from subsurface waters but will not include methods for
we I I construction.
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Sect i on 3.2
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3.2 SURFACE WATERS
The choice of sample locations in surface waters is an important
consideration which must be addressed prior to sample acquisition, since
it will often effect the selection of sampling equipment. Selection of
representative locations will depend on many factors including stream
dimensions, shape, flow rate (velocity), imputs and discharges. The USGS
publishes the national Handbook of Recommended Methods for Water Data
Acquisition which addresses this problem in detail, in addition to several
other concepts including flow measurement.
Generally the selection of sample locations will be detailed in the
sampling plan, however familiarity with the concepts in the USGS Handbook will
assist the samplers in accommodating in-field adjustments. Most often depth
integrated and/or cross-sectional composite samples are preferable to
single-point grabs. In practice safe access and handling as well as other
physical limitations will be influential factors during sample acquisition at
hazardous waste contaminated sites.
Samples from shallow depths can be readily collected by merely submerging
the sample container. The method is advantageous when the sample might be
significantly altered during transfer from a collection vessel into another
container. This is the case with samples collected for oil and grease analysis
since considerable material may adhere to the sample transfer container and as
a result produce inaccurately low analytical results. Similarly the transfer
of a liquid into a small sample container for volatile organic analysis, if not
done carefully, could result in significant aeration and resultant loss of
volatile species. Though simple, representative, and generally free from
substantial material disturbances, it has significant shortcomings when applied
to a hazardous waste, since the external surface of each container would then
need to be decontaminated.
In general the use of a sampling device, either disposable or constructed
of a nonreactive material such as glass, stainless steel, or Teflon, is the
most prudent method. The device should have a capacity of at least 500 ml, if
possible, to minimize the number of times the liquid must be disturbed, thus
reducing agitation of any sediment layers.
A 1-liter stainless steel beaker with pour spout and handle works well.
It is easily cleaned and considerably less expensive than Teflon. Though still
more expensive than other plastics it is more durable and generally more inert
under field conditions. Also useful are large stainless steel ice scoops and
ladles available from commercial kitchen and laboratory supply houses.
It is often necessary to collect liquid samples at some distance from
shore or the edge of the containment. In this instance an adaptation which
extends the reach of the technician is advantageous. Such a device is the
pond sampler as devised by the California Department of Health.2 It
incorporates a telescoping heavy-duty aluminum pole with an adjustable beaker
clamp attached to the end (see Method III-2). The beaker previously
3-2
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Section 3.2
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described, a disposable glass or plastic container, or the actual sample
container itself, can be fitted into the clamp. In situations where cross
contamination is of concern, use of a disposable container or the actual sample
container is always advantageous. The cost of properly cleaning usually
outweighs the cost of disposal of otherwise reusable glassware or bottles.
This is especially true when the cleanup must be done in the field. The
potential contamination of samples for volatile organic analysis by the mere
presence of organic solvents necessary for proper field cleaning is usually too
great to risk.
Another method of extending the reach of sampling efforts is the use of a
small peristaltic pump (see Method I I 1-3). In this method the sample is drawn
in through heavy-wall Teflon tubing and pumped directly into the sample
container. This system allows the operator to reach out into the liquid body,
sample from depth, or sweep the width of narrow streams.
If a medical grade silicone tubing is used in the peristaltic pump,
the system is suitable for sampling almost any parameter including most
organics.34Some volatile stripping, however, may occur, and though the system
may have a high flow rate, some material may be lost on the tubing. Therefore,
pumping methods should be avoided for sampling volatile organics or oil and
grease. Battery-operated pumps of this type are available and can be easily
hand-carried or carried with a shoulder sling. It is necessary in most
situations to change both the Teflon suction line as well as the silicon pump
tubing between sample locations to avoid cross-contamination. This requires
maintaining a sufficiently large stock of material to avoid having to clean the
tubing in the field.
These tubings are quite expensive but their relatively inert nature makes
thorough decontamination in the lab both practical and simple thus allowing
reuse. It should be noted that the Teflon suction tubing is an effective
substitute for that supplied with the sophisticated automatic liquid waste
samplers such as the I SCO Model 2100 and Manning Models S-3000 and S-4040.
When medical grade silicon tubing is not available or the analytical
requirements are particularly strict, the system can be altered as described
in Method III-3, Figure 3-3. In this configuration the sample volume
accumulates in the vacuum flask and does not enter the pump. The integrity
of the collection system can now be maintained with only the most nonreactive
material contacting the sample. Some loss in I ift abi I ity wi I I result since
the pump is now moving air, a compressible gas rather than an essentially
noncompress i bIe liquid.
It may on occasion be necessary to sample large bodies of water where
a near surface sample will not sufficiently characterize the body as a whole.
In this instance again the above-mentioned pump is quite serviceable. It is
capable of lifting water from depths in excess of 6 meters. Since the lift
capacity is actually measured as the distance above the hydrostatic surface, it
is possible to withdraw samples from depths significantly below the water
surface. It should be noted that this lift ability decreases somewhat with
higher density fluids and with increased wear on the silicone pump tubing.
3-3
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Section 3.2
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Page 3 of 3
Similarly increases in altitude will decrease the pumps ability to lift from
depth. When sampling a liquid stream which exhibits a considerable flow rate,
it may be necessary to weight the bottom of the suction line. The stainless
steel strainer suction weight supplied with the I SCO and Manning samplers
usually works well. A heavier weight can be constructed by filling a short
(7.5 cm to 10 cm) length of Teflon tubing with lead and plugging both ends with
tight-fitting Teflon plugs. This weight can then be clamped with stainless
steel band clamps to the suction tubing.
Situations may still arise where a sample must be collected from depths
beyond the capabilities of a peristaltic pump. In this instance an at-depth
sampler may be required, such as a Kemmerer, ASTM Bomb (Bacon Bomb) or Van Dorn
sampler. These devices work well; however, care must be utilized in selecting
devices that are made of materials that will not contaminate the sample. Van
Dorn samplers are not generally recommended for organics as they rely on an
elastic closing mechanism that can effect samples. They are readily available
in a totally nonmetallic design which is very useful for sample collection for
trace metal analysis.
Kemerer samplers are available on special order or adaptable for sample
collection for organic analysis by substituting Teflon for the rubber or
plastic stoppers. If the device is further ordered with stainless steel
metal I ic parts in addition to Teflon stoppers it becomes a very versati le
sampler.
The submersible pumps discussed in conjunction with groundwater sampling
(Section 3.4) may also be useful in this application.
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Section 3.2.1
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Page 1 of 2
3.2.1 METHOD I I 1-1: SAMPLING SURFACE WATERS USING A DIPPER OR
OTHER TRANSFER DEVICE
Discussion
A dipper or other container constructed of inert material, such as
stainless steel or Teflon, can be used to transfer liquid wastes from their
source to a sample bottle. This prevents unnecessary contamination of the
outer surface of the sample bottle that would otherwise result from direct
immersion in the liquid. Use of this device also prevents the technician from
having to physically contact the waste stream. Depending upon the sampling
application, the transfer vessel can be either disposed of or reused. If
reused, the vessel should be thorougly rinsed and/or decontaminated prior to
sampling a different source.
Uses
A transfer device can be utilized in most sampling situations except where
aeration must be eliminated (samples for volatile organic analysis) or where
significant material may be lost due to adhesion to the transfer container.
Procedures for Use
1. Submerge a precleaned stainless steel dipper or other suitable device
with minimal surface disturbance.
2, Allow the device to fill slowly and continuously.
3. Retrieve the dipper/device from the surface water with minimal
d isturbance.
4, Remove the cap from the sample bottle and slightly tilt the mouth of
the bottle below the dipper/device edge.
5, Empty the dipper/device slowly, allowing the sample stream to flow
gently down the side of the bottle with minimal entry turbulence.
6, Continue delivery of the sample until the bottle is almost completely
filled. Leave adequate ullage to allow for expansion.
7, Select appropriate bottles and preserve the sample if necessary as
per guidelines in Appendix A.
8. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
9, Label the sample bottle with an appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Record the information in the field logbook and
complete the chain-of-custody form.
3-5
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Section 3.2.1
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Page 2 of 2
10. Properly clean and decontaminate the equipment prior to reuse or
storage (Appendix E).
Sources
GCA Corporation, "Quality Assurance Plan, Love Canal Study - Appendix A,
Sampling Procedures," EPA Contract 68-02-3168.
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Section 3.2.2
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Page 1 of 3
3.2.2 METHOD III-2: USE OF POND SAMPLER FOR THE COLLECTION
OF SURFACE WATER SAMPLES
Discussion
The pond sampler consists of an adjustable clamp attached to the end of a
two- or three-piece telescoping aluminum tube that serves as the handle. The
clamp is used to secure a sampling beaker (see Figure 3-1). The sampler is not
commercially available, but it is easily and inexpensively fabricated. The
tubes can be readily purchased from most hardware or swimming pool supply
stores. The adjustable clamp and sampling beaker can be obtained from most
laboratory supply houses. The materials required to fabricate the sampler are
given in Appendix B.
Uses
The pond sampler is used to collect liquid waste samples from disposal
ponds, pits, lagoons, and similar reservoirs. Grab samples can be obtained at
distances as far as 3.5 m from the edge of the ponds. The tubular aluminum
handle may bow when sampling very viscous liquids if sampling is not done
s I ow I y.
Procedures for Use
1. Assemble the pond sampler. Make sure that the sampling beaker and
the bolts and-nuts that secure the clamp to the pole are tightened
properly.
2, With proper protective garment and gear, take grab samples by slowly
submerging the precleaned beaker with minimal surface disturbance.
3, Retrieve the pond sampler from the surface water with minimal
d isturbance.
4, Remove the cap from the sample bottle and slightly tilt the mouth of
the bottle below the dipper/device edge.
5, Empty the sampler slowly, allowing the sample stream to flow gently
down the side of the bottle with minimal entry turbulence.
6, Continue delivery of the sample until the bottle is almost completely
fi I led.
7. Select appropriate sample bottles and preserve the sample if
necessary as per guidelines in Appendix A.
8, Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
3-7
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Section 3.2.2
Rev i s i on 0
Page 2 of 3
Varlgrip clamp
Bolt hole
Beaker, stainless
steel or disposable
Pole, telescoping, aluminum, heavy
duty, 250-450 cm (96-180")
Source: Reference 1 .
Figure 3-1. Pond sampler.
Q Q
o-o
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10.
Sources
Section 3.2.2
Revision 0
Page 3 of 3
9, Label the sample bottle with an appropriate sample tag. Be sure to
label the tag carefully and clearly, addressing all the categories
or parameters. Record the information in the field logbook and
complete the chain-of-custody documents.
Properly clean and decontaminate the equipment prior to reuse or
storage using recommended guidelines of Appendix E.
deVera, E.R.,
and Sampling
January 1980.
Simmons,
Procedures
.P., Stephens, R.D.
for Hazardous Waste
and Storm, D.L. "Samplers
Streams," EPA-600/2-80-018,
GCA Corporation, "Quality Assurance Plan, Love Canal
Sampling Procedures," EPA Contract 68-02-3168.
Study - Appendix A,
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Sect i on 3.2.3
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Page 1 of 4
3.2.3 METHOD III-3: PERISTALTIC PUMP FOR SAMPLING SURFACE WATER BODIES
Discussion
This collection system consists of a peristaltic pump capable of
achieving a pump rate of 1 to 3 Ipm, and an assortment of Teflon tubing for
extending the suction intake. A battery operated pump is preferable as it
eliminates the need for DC generators or AC inverters.
The system, as shown in Figures 3-2 and 3-3, is highly versatile. It is
portable and the sample collection is conducted through essentially chemically
nonreactive material. It is practical for a wide range of applications
including streams, ponds, and containers. This procedure can both extend the
lateral reach of the sampler and allow sampling from depth. Likewise, it can
function both as a well purge and a sample collection system. The chief
disadvantage of this method is the limited lift capacity of the pump,
approximately 8 meters.
Procedures for Use
1. Install clean, medical-grade silicone tubing in the pump head, as
per the manufacturer's instructions. Allow sufficient tubing on
discharge side to facilitate convenient dispensation of liquid into
sample bottles and only enough on the suction end for attachment to
the intake line. This practice will minimize sample contact with the
si I icone pump tubing.
2, Select the length of suction intake tubing necessary to reach the
required sample depth and attach to intake side of pump tubing.
Heavy-wall Teflon, of a diameter equal to the required pump tubing,
suits most applications. (Heavier wall will allow for a slightly
greater lateral reach.)
3. If possible, allow several liters of sample to pass through system,
before actual sample collection. Collect this purge volume and then
return to source after the sample aliquot has been withdrawn.
4, Fill necessary sample bottles by allowing pump discharge to flow
gently down the side of bottle with minimal entry turbulence. Cap
each bottle as fi I led.
5, Select appropriate bottles and preserve the sample if necessary as
per guidelines in Appendix A.
6, Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
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Page 2 of 4
60
e
a
E
a
CO
0)
u
c
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Section 3.2.3
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TEFLON CONNECTOR
6 MM I. D.
GLASS TUBING
6 MM O.D.
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Section 3.2.3
Rev i s i on 0
Page 4 of 4
7, Label the sample bottle with an appropriate tag. Be sure to complete
the tag with all necessary information. Record the information in
the field logbook and complete the chain-of-custody documents.
Allow system to drain, then disassemble. Return tubing to lab for
decontamination (if feasible). See Appendix E for general
decontamination procedures.
Sources
U.S. Environmental Protection Agency. "Procedures Manual for Ground Water
Monitoring at Solid Waste Disposal Facilities." EPA-530/SW-611. August
1977.
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3.2.4 METHOD III-4: COLLECTION OF WATER SAMPLES FROM DEPTH WITH A
KEMMERER BOTTLE
Discussion
The kemmerer bottle is a messenger-activated water sampling device (see
Figure 3-4). In the open position water flows easily through the device.
Once lowered to the desired depth a messenger is dropped down the sample line
tripping the release mechanism and closing the bottle. In the closed position
the bottle is sealed, both on top and bottom, from any additional contact with
the water column and can be retrieved.
Most commercially available Kemmerer bottles are of brass or plastic
construction. Modification of existing systems with nonreactive materials such
as Teflon, glass or stainless steel would be only partially successful due to
the complicated machining necessary for the release mechanism. Other
modifications such as a stoppered bottom drain are simpler and useful in
minimizing sample disturbance during transfer to the appropriate containers.
Uses
The Kemmerer bottle is currently the most practical method of collecting
discrete, at-depth samples from surface waters or vessels where the collection
depth exceeds the lift capacity of pumps. The application is limited however
by the incomparabi I ity of various construction materials with some analytical
techniques. Proper selection, i.e., all metal assemblies for organic analysis
or all plastic assemblies for trace element analysis, will overcome this
deficiency.
Procedures for Use
1. Inspect Kemmerer bottle for thorough cleaning and insure that sample
drain valve is closed (if bottle is so equipped).
2, Measure and then mark sample line at desired sampling depth.
3, Open bottle by lifting top stopper-trip head assembly.
4. Gradually lower bottle until desired level is reached (predesignated
mark from Step 2).
5, Place messenger on sample line and release.
6, Retrieve sampler; hold sampler by center stem to prevent accidental
opening of bottom stopper.
7. Rinse or wipe off exterior of sampler body (wear proper gloves and
protective clothing).
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Sect i on 3.2.4
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Page 2 of 3
MESSENGER
CABLE
TRIP HEAD
UPPER STOPPER
CHAIN
CENTER ROD
BODY
BOTTOM
DRAIN
LOWER STOPPER
Figure 3-4. Modified Kemmerer sampler.
3-15
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Sect i on 3.2.4
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Page 3 of 3
8, Recover sample by grasping lower stopper and sampler body with one
hand (gloved), and transfer sample by either (a) lifting top stopper
with other hand and carefully pouring contents into sample bottles,
or (b) holding drain valve (if present) over sample bottle and
opening valve.
9, Allow sample to flow slowly down side of sample bottle with minimal
d isturbance.
10. Select sample bottles and preserve the sample if necessary as per
guidelines in Appendix A.
11. Check that a Teflon liner is present in the cap if required. Secure
the cap tightly.
12. Label the sample bottle with an appropriate tag. Be sure to complete
the tag with all necessary information. Record the information in
the field logbook and complete all chain-of-custody records.
13, Decontaminate sampler and messenger or place in plastic bag for
return to lab. See Appendix E for general decontamination
procedures.
Sources
U.S. Environmental Protection Agency, "Procedures Manual for Ground Water
Monitoring at Solid Waste Disposal Facilities." EPA-530/SW-611, August
1977.
3-I6
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Sect i on 3.3
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Page 1 of 2
3.3 CONTAINERIZED LIQUIDS
The sampling of tanks, containers, and drums present unique problems not
associated with natural water bodies. Containers of this sort are generally
closed except for small access ports, manways, or hatches on the larger
vessels or taps and bungs on smaller drums. The physical size, shape,
construction material, and location of access will limit the types of
equipment and methods of collection.
When liquids are contained in sealed vessels, gas vapor pressures build
up, sludges settle out, and density layer ings develop. The potential for
explosive reactions or the release of noxious gases when containers are opened
requires considerable safeguards. The vessels should be opened with extreme
caution. Preliminary sampling of any headspace gases may be warranted.
Section 4.4 details procedures for sampling headspace gases. As a minimum, a
preliminary check with an organic vapor analyzer may help determine needed
levels of personnel protection and may be of aid in selecting a sampling method.
In most cases it is impossible to observe the contents of these sealed or
partially sealed vessels. Since some layering or stratification is likely in
any solution left undisturbed over time, a sample must be taken that represents
the entire depth of the vessel.
Agitation to disrupt the layers and rehomogenize the sample is physically
difficult and almost always undesirable. In vessels greater than 1 meter in
depth the method of choice is to slowly, in known increments of length, lower
the suction line from a peristaltic pump. Discrete samples can be collected
from various depths then combined or analyzed separately. If the depth of the
vessel is greater than the lift capacity of the pump, an at-depth water sampler,
such as the Kemmerer type discussed in Method III-4, or the ASTM Bomb (Bacon
Bomb) may be required. In situations where the reactive nature of the contents
are known, a small submersible pump may be used.
When sampling a previously sealed vessel, a check should be made for the
presence of a bottom sludge. This is easily accomplished by measuring the
depth to apparent bottom then comparing it to the known interior depth.
Methods for sampling a bottom sludge are found in Section 2.3.
The sampling of drums for hazardous liquid wastes is a very taxing
situation with present equipment. The most widely used method is a glass tube,
6 mm to 16 mm I.D, that is lowered into the drum. The top of the tube is
sealed with a stopper or the thumb and the tube withdrawn. The bottom of the
tube is then placed over a glass jar, the stopper removed from the top and
the contents drained into the containers. After collection of sufficient
sample the tube is then broken up into the drum. This method is simple,
relatively inexpensive, and quick and collects a sample without having to
decontaminate equipment. It does, however, have serious drawbacks. Most low
density fluids do not hold we I I in the glass tubes. A great deal of the
potential sample flows out of the bottom of the tube as it is raised from the
drum, thereby reducing the representativeness of collected material. Many
3-I7
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Page 1 of 3
3.3.1 METHOD III-5: COLLECTION OF LIQUID CONTAINERIZED
WASTES USING GLASS TUBES
Description
Liquid samples from opened containers (55-gallon drums) are collected
using lengths of glass tubing. The glass tubes are normally 122 cm in length
and 6 to 16 mm inside diameter. Larger diameter tubes may be used for more
viscous fluids if sampling with the small diameter tube is not adequate. The
tubing is broken up and discarded in the container after the sample has been
collected, eliminating difficult cleanup and disposal problems. This method
should not be attempted with less than a two-man sampling team.
Uses
This method provides for a quick, relatively inexpensive means of
collecting concentrated containerized wastes. The major disadvantage is from
potential sample loss which is especially prevalent when sampling less viscous
fluids. Splashing can also be a problem and proper protective clothing (e.g.,
butyl rubber apron, face shields, boot covers) should always be worn.
Procedures for Use
1. Remove cover from sample container opening.
2, Insert glass tubing slowly to a I most the bottom of the container.
Try to keep at least 30 cm of tubing above the top of the container.
3, Allow the waste in the drum to reach its natural level in the tube.
4, Cap the top of the tube with a safety-gloved thumb or a rubber
stopper.
5, Carefully remove the capped tube from the drum and insert the
uncapped end in the sample container.
6. Release the thumb or stopper on the tube and allow the sample
container to fill to approximately 90 percent of its capacity.
7, Repeat steps 2 through 6 if more volume is needed to fill the sample
container.
8. Remove the tube from the sample container and replace the tube in the
drum.
9, Cap the sample container tightly with a Teflon-lined cap and affix
the sample identification tag.
10. Break the glass sampling tube in such a way that all parts of it are
discarded inside the drum. (Note: see the initial discussion to
this section for exceptions.)
3-I8
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Sect i on 3.3
Rev i s i on 0
Page 2 of 2
variations to this technique have been reported. These include the
incorporation of a small suction device (i.e., pipette bulb) to the top of the
tube as well as the use of various tube sizes. Some success has been reported
with tubes that have been heated at one end then drawn to form a much smaller
orifice. This allows the use of larger diameter tubing, therefore a greater
volume of sample per attempt, while reducing the material loss from the tube
bottom normally associated with larger diameter tubes.
It should be noted that in some instances disposal of the tube by breaking
it into the drum may interfere with eventual plans for the removal of its
contents. The use of this technique should therefore be cleared with the
project officer, or other disposal techniques evaluated.
In many instances a drum containing waste material will have a sludge
layer on the bottom (Method I I 1-5). Slow insertion of the sample tube down
into this layer and then a gradual withdrawal will allow the sludge to act as
a bottom plug to maintain the fluid in the tube. The plug can be gently
removed and placed into the sample container by the use of a stainless steel
lab spoon. These spoons are relatively inexpensive and can be disposed of in
the original waste container with the glass transfer tube.
Designs exist for equipment that will collect a sample from the full
depth of a drum and maintain it in the transfer tube until delivery to the
sample bottle. These designs include primarily the Composite Liquid Waste
Sampler (COLIWASA) and modifications thereof.2 The COLIWASA is difficult to
properly decontaminate in the field; its applicability is therefore limited to
those cases when a sample of the full depth of the drum is absolutely
necessary. The COLIWASA can be somewhat modified for this task by making the
lift rod of stainless steel, the bottom stopper of Teflon, and the body of
glass tubing. In this configuration the glass tube can be broken into the
drum leaving only the center rod and the stopper to be decontaminated. In a
preliminary investigation where the total number of drums to be sampled is
small an equal number of both the center rods and bottom stoppers could be
made in advance thus eliminating the time involved for onsite cleanup. Heat
shrinkable Teflon tubing or other types of Teflon coating can also be used to
cover the stainless steel rod if contact of the stainless steel with the waste
is undesirable.
3-19
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Section 3.3.1
Rev i s i on 0
Page 3 of 3
3, When a solid is encountered in a drum (either layer or bottom
sludge) the optional method described above may be used to collect
a core of the material, or the material may be collected with a
disposable scoop attached to a length of wooden or plastic rod.
4, If analysis is to be performed onsite, packing steps 12 and 13 may be
deleted. These steps are necessary for transporting and/or shipping
samples.
Sources
American Society for Testing and Materials. "Standard Recommended
Practices for Sampling Industrial Chemicals," ASTM E-300-73.
U.S. Environmental Protection Agency, "Technical Methods for Investigating
Sites Containing Hazardous Substances, Technical Monograph 1-29, Draft,"
Ecology and the Environment, June 1981.
3-20
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Section 3.3.1
Revision 0
Page 2 of 3
11. Replace the bung or place plastic over the drum.
12. Place sample container in a Ziplock plastic bag (one per bag).
13. Place each bagged container in a l-gallon metal paint can (or
appropriate sized container) and pack in vermiculite packing
material. Place I id on the can.
14. Mark the sample identification number on the outside of each paint
can and complete chain-of-custody log and the field logbook.
Optional Method (if sample of bottom sludge is desired)
1. Remove cover from container opening.
2, Insert glass tubing slowly almost to the bottom of the container.
Try to keep at least 30 cm of tubing above the top of the container.
3, Allow the waste in the drum to reach its natural level in the tube.
4, Gently push the tube towards the bottom of the drum into the sludge
layer. Do not force it.
5. Cap the top of the tube with a safely-gloved thumb or rubber stopper.
6, Carefully remove the capped tube from the drum and insert the
uncapped end in the sample container.
7, Release the thumb or stopper on the tube and allow the sample
container to fill to approximately 90 percent of its capacity. If
necessary, the sludge plug in the bottom of the tube can be dislodged
with the aid of a stainless steel laboratory spatula.
8, Repeat if more volume is needed to fill sample container and recap
the tube.
9. Proceed as in Steps 9 through 14 above.
Note:
1. If a reaction is observed when the glass tube is inserted (violent
agitation, smoke, light, heat, etc.) the investigator should leave
the area immediately.
2, If the glass tube becomes cloudy or smokey after insertion into the
drum, the presence of hydrofluoric acid is indicated and a
comparable length of rigid plastic tubing should be used to collect
the sample.
3-2I
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Section 3.3.2
Revision 0
Page 1 of 3
3.3.2 METHOD III-6: SAMPLING CONTAINERIZED WASTES USING THE
COMPOSITE LIQUID WASTE SAMPLER (COLIWASA)
Discussion
The COLIWASA is a much cited sampler designed to permit representative
sampling of multiphase wastes from drums and other containerized wastes.
The sampler is commercially available or can be easily fabricated from a
variety of materials including PVC, glass, or Teflon. In its usual
configuration it consists of a 152 cm by 4 cm (inside diameter) section of
tubing with a neoprene stopper at one end attached by a rod running the length
of the tube to a locking mechanism at the other end. Manipulation of the
locking mechanism opens and closes the sampler by raising and lowering the
neoprene stopper. A current recommended model of the COLIWASA is shown in
Figure 3-5; however, the design can be modified and/or adapted somewhat to meet
the needs of the sampler.
Uses
The COLIWASA is primarily used to sample most containerized liquids. The
plastic COLIWASA is reported to be able to sample most containerized liquid
wastes except for those containing ketones, nitrobenzene, dimethylforamide,
mesityloxide and tetrahydrofuran. A glass COLIWASA is able to handle all
wastes unable to be sampled with the plastic unit except strong alkal i and
hydrofluoric acid solution. Due to the unknown nature of most containerized
waste, it would therefore be advisable to eliminate the use of PVC materials
and use samplers composed of glass or Teflon.
The major drawbacks associated with using a COLIWASA concern
decontamination and costs. The sampler is difficult if not impossible to
decontaminate in the field and its high cost in relation to alternative
procedures (glass tubes) make it an impractical throwaway item. It still has
applications, however, especially in instances where a true representation of a
multiphase waste is absolutely necessary. For this reason, the procedure for
its use is included.
Procedures for Use
1. Choose the material (see Appendix B) to be used to fabricate the
COLIWASA and assemble the sampler as shown in Figure 3-5.
2, Make sure that the sampler is clean.
3, Check to make sure the sampler is functioning properly. Adjust the
locking mechanism if necessary to make sure the neoprene rubber
stopper provides a tight closure.
4, Wear necessary protective clothing and gear and observe required
samp I ing precautions.
3-22
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Section 3.3.2
Rev i s i on 0
Page 3 of 3
5, Put the sampler in the open position by placing the stopper rod
handle in the T-position and pushing the rod down until the handle
sits against the sampler's locking block.
6, Slowly lower the sampler into the liquid waste. (Lower the sampler
at a rate that permits the levels of the liquid inside and outside
the sampler tube to be about the same. If the level of the I iquid in
the sample tube is lower than that outside the sampler, the sampling
rate is too fast and will result in a nonrepresentative sample).
7, When the sampler stopper hits the bottom of the waste container, push
the sampler tube downward against the stopper to close the sampler.
Lock the sampler in the closed position by turning the T handle until
it is upright and one end rests tightly on the locking block.
8, Slowly withdraw the sampler from the waste container with one hand
while wiping the sampler tube with a disposable cloth or rag with the
other hand.
9, Carefully discharge the sample into a suitable sample container by
slowly pulling the lower end of the T handle away from the locking
block while the lower end of the sampler is positioned in a sample
conta iner.
10. Cap the sample container with a Teflon-lined cap; attach label and
seal; record in field logbook; and complete sample analysis request
sheet and chain-of-custody record.
11. Unscrew the T handle of the sampler and disengage the locking block.
Clean sampler onsite or store the contaminated parts of the sampler
in a plastic storage tube for subsequent cleaning. Store used rags
in plastic bags for subsequent disposal. See Appendix E for general
decontamination procedures.
Sources
deVera, E. R., Simmons, B. P., Stephens, R. D., and Storm, D. L. "Samplers
and Sampling Procedures for Hazardous Waste Streams." EPA 600/2-80-019,
January 1980.
3-23
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K 2.86 cm (1 1/8")
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4.26 en (1 7/8") O.D.
C *._.»»_.. _A.J t»f^«
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Source: Reference 6.
Figure 3-5. Composite liquid waste sampler (Coliwasa).
GO
hO
-------
3.4 GROUNDWATER
Section 3.4
Revision 0
Page 1 of 7
Groundwater sampling suffers from many of the same difficulties as closed
containers, such as the inability to observe what is being collected or what
disturbances are resulting from that collection.
There are essentially two sources from which to collect groundwater,
either from wells or from seeps and springs. The former is more complex and a
discussion of its intricacies will follow later. The sampling of seeps and
springs is considerably easier, but it may be less indicative of the actual
groundwater quality than well sampling.
Seeps and springs are generally areas where the surface contour intersects
the water table. These areas usually have well established microbiological
populations evidenced by extensive moss and algal growths. These
microbiological populations usually extend for some distance into the
water-bearing formation (aquifer) and are generally more populous and of
different species than those associated with the bulk of the aquifer. Their
effect on the oxygen content, pH, nutrient and metals concentrations in the
groundwater can be extensive. The water, therefore, that seeps from these
areas may be substantially altered, and not representative of the conditions
deeper in the subsurface. They can, however, yield some information if
properly interpreted. If the area in question is without developed wells they
are certainly worth consideration, especially for the ease with which they can
be sampled.
A stainless steel scoop of the type found in ice machines is ideal for
collecting samples from seeps. The flat bottom can be pressed against the bank
and the water will flow with very little additional disturbance into the scoop,
for transfer to the sample bottles. It is important to collect the sample as
close to the actual seep as possible to reduce contact time with the atmosphere
and potential for surface contamination.
For the purposes of this document, groundwater monitoring via wells will
include only the actual sampling of existing wells. The methods and techniques
for placement, construction, and development of wells for groundwater
monitoring are varied and complicated. The "Manual for Ground-Water Sampling
Procedures"6and "NEIC Manual for Groundwater/Subsurface Investigations at
Hazardous Waste Sites"7provide considerable information for establishing a
full groundwater monitoring program including the completion of monitor wells.
It is, however, necessary to know the well depth, diameter, construction
material, type and size of the well screen if used, vertical position of the
well screen or slotted section of casing, and type of annular packing if any.
This information will aid in evaluating the suitability of the well for
sampling for a particular analysis. For instance, if the well has a galvanized
steel casing with a brass well screen, it would not be suitable for trace
element analysis. Similarly, if the well is located in a swampy area, the
type and amount of grout or fill around the well casing would determine the
degree of surface water inflow to the we I I that might be expected. Most of
the information necessary is available on the well drillers log. An example
of a completed drillers log is included as Figure 3-6. It should be noted,
3-25
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Sect i on 3.4
Revision 0
Page 2 of 7
OBSERVATION WELL CONSTRUCTION SUMMARY
PftMCCT
WTC _
OQOftMNATCS n
DATE COMFLCTCO
SUPCRVISCD §Y _
10/27/82
P. Huidobro
WELL HO.
FB137
Glacial Drift
AQUIFM
0KOUNO
CLCVATION
..
'1*
v ' ^
lopsoi
Peat
Alternating
layers of gray M
till and outwaab
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i2
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JU twain
Cray till
tedium aand vlth
pebbly gravel
.i»e«tone bedrock
Elevation of reference point
Height of reference point above
ground surface
Depth of turface seal
Type of surface seal: coacrete
910.9
1.76
1.0. of surface casing
Type of surface casing: Steel vith
vented locking cap
4"
(Depth of surface casing
I.D. of riser pipe
Type of riser pipe: galvanised atael
5.241
{Diameter of borehole
1/1 cement/bentonite
4"
Type of filler:
Elevation / depth of top of seal
Type of seal: 1/1 ceaent/bentotiit*
834.54/74.6'
. , , .ailica aand No. 20
Type of grave. P«, 833.54'/75.6'
Elev./depth of top of gravel pack
Elevation / depth of top of screen
Beicfiption of screen «O. 10 SIO
welded galvanized steel
826.84-/82.31
rot
I.D. of screen section
Elevation / depth of bottom of screen
Elev./depth of bottom of gravel pack
Elev./depth of bottom of plugged
blank section
-JType of filler below plugged
section _
-{Elevation of bottom of borehole
822.64'/86.5*
822.64V86.5'
822.64-/86.51
822.64V86.5'
Form 1002
Figure 3-6. Sample well construction form.
3-26
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Sect i on 3.4
Rev i s i on 0
Page 3 of 7
however, that the actual well depth may be somewhat less than the completion
depth listed on the log as a result of aquifer invasion through the screen or
open-hole sloughing below the casing. This may be particularly noticable in
wells that have had only sporadic use or have been idle long. It is
recommended then that actual well depth be checked by field measurement
whenever possible.
Measurement of the well depth can be accomplished by sounding the well
with a reusable weight attached to a disposable line. Slowly lower the weight
into the well until the bottom is detected. With the line taut, mark the top
of casing level on the line with waterproof ink. Recover the line and weight
from the well and accurately measure the length of line below the mark.
Discard the line and thoroughly clean the weight before reuse. Next, measure
the casing length above (or below) ground level and subtract (or add) to obtain
well depth.6When measuring potentially contaminated wells, wear appropriate
safety gear to avoid skin contact with well water.
The depth to the water level in the well must be measured in order to
calculate the liquid bore volume for prepurging and is also important to any
hydro logical interpretations of the analytical results. Depths to water are
normally measured with respect to the top of casing, as in well-depth
determinations. Several methods are available including: (1) the electric
sounder, (2) the chalked steel tape, and (3) the popper.6
The electric sounder, although not the most accurate, is recommended for
initial site work because of the minimal potential for equipment contamination
and simplicity of use. Sounders usually consist of a conductivity cell at the
end of a graduated wire, and a battery powered buzzer. When the cell contacts
the water the increased conductivity completes the circuit and allows current
to flow to the alarm buzzer. The depth to water can then be read from the
graduations on the wire or the wire can be measured directly. This device may
not be suitable for use if a potentially flammable or explosive layer is
present in the well, unless it is an intrinsically safe version. A discussion
of electrical product certification is presented in Appendix F.
The chalked steel tape is a more accurate device for measuring static
water levels. Coat the lower 0.5 to 1.0 meters of a steel measuring tape on
either side with either carpenter's chalk or any of the various indicating
pastes. Attach a weight to the lower end to keep the tape taut and lower it
into the center of the well (condensate on the casing wall may prematurely
wet the tape). Listen for a hallow "plopping" sound when the weight reaches
water. Then lower the tape very slowly for at least another 15 cm, preferably
to an even increment. Next, carefully withdraw the tape from the well;
determine water depth by subtracting the wetted length of tape from the total
length of tape in the well. In smaI I-diameter wells, the volume of the weight
may cause the water to rise by displacement. In general the use of indicating
paste or chalk should be discouraged although they may not present a
significant problem if water samples are not collected. As with all depth
measurement devices, thoroughly clean the wetted section of the tape and the
weight before reuse to avoid cross contamination.
3-27
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Section 3.4
Revision 0
Page 4 of 7
The metal tape and popper is another simple and reliable method for
measuring depth to water in wells more than 3.8 cm (1.5 in.) in diameter. The
popper is a metal cylinder with a concave undersurface fastened to the end of
the metal tape. Raise and drop the popper until it hits the water surface and
makes a distinct "popping" sound. Adjust the tape length so that the popper
just hits the water surface. Read the depth to water from the tape measure.
To obtain a representative sample of the groundwater it must be understood
that the composition of the water within the well casing and in close proximity
to the well is probably not representative of the overall groundwater quality
at that sampling site. This is due to the possible presence of drilling
contaminants near the well and because important environmental conditions such
as the oxidation-reduction potential may differ drastically near the well from
the conditions in the surrounding water-bearing materials. For these reasons
it is highly desirable that a well be pumped or bailed until the well is
thoroughly flushed of standing water and contains fresh water from the aquifer.
The recommended amount of purging before sampling is dependent on many factors
including the characteristics of the well, the hydrogeological nature of the
aquifer, the type of sampling equipment being used, and the parameters being
sampled. A common procedure is to pump or bail the well until a minimum of two
(2) to ten (10) bore-volumes have been removed.
Gibb8notes that removing all water from the well bore is only possible
if the well is pumped dry and suggests two alternative approaches: (a)
monitor the water level in the well while pumping. When the water level has
"stabilized" most if not all of the water being pumped is coming from the
aquifer, (b) monitor the temperature, conductivity, or pH of the water while
pumping. When these parameters "stabilize" it is probable that little or no
water from casing storage is being pumped.5
The use of an indicating analysis such as pH, temperature, redox
potential, or, most commonly, conductivity, may be the most accurate and
reliable method of assuring complete well purging and it also reduces the
likelihood of over overpurging. The technique is easily implemented in the
field and gives a rapid and positive indication of changes in the well bore
water. This change in the water character and subsequent stabilization can
normally be interpreted as evidence that sufficient purging has occurred. It
should be noted that the sensitivity of these parameters to changes as a
result of exposure of groundwater to surface level conditions (i.e., changes
in the partial pressure of dissolved gases or the conditions of the purging
system) make in-situ monitoring desirable. An alternative to this would be
to conduct these measurements in a closed cell attached to the discharge
s i de of the pump system.
Other factors which will influence the amount of purging required before
sampling include the pumping rate and the placement of the pumping equipment
within the column of water in the well bore. For example, recent studies
have shown that if a pump is lowered immediately to the bottom of a well
before pumping, it may take some time for the column of water above it to be
exchanged if the transmissivity of the aquifer is high and the well screen
3-28
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Sect i on 3.4
Revision 0
Page 5 of 7
is at the bottom of the casing.58 In such cases the pump will be drawing
water primarily from the aquifer.
This has been further documented in studies conducted by the National
Council of the Paper Industry for Air and Stream Improvement (NCASI)4on a
full-scale model of a 2-inch PVC well. They found that purging from just
below the water surface insured a more complete removal of the casing water
than by withdrawal from well below the surface. It was also evident that when
purging did occur from just below the surface, satisfactory results could be
obtained at any of a wide range of pumping rates with either a peristaltic or
a submersible pump.
Because of the potential for further environmental contamination,
planning for purge water disposal is a necessary part of well monitoring.
Alternatives range from dumping it on the ground (not back down the well) to
full containment, treatment, and disposal. If the well is believed to be
contaminated, the best practice is to contain the purge water and store it
until the water samples have been analyzed. Once the contaminants are
identified, appropriate treatment requirements can be determined.
There are many methods available for well purging. In some cases bailing
will suffice, however it can become tedious and labor intensive in deep or
large diameter wells. In some situations, an inflatable packer can be
utilized above and/or below the pump to reduce the casing volume requiring
purging. This technique is particularly adaptable to wells with more than one
screened interval to isolate the aquifer of interest. The size and weight of a
pump and packer assembly usually require tripods/derricks and hoist equipment
which are not easily implemented. Additionally the packer may be constructed
of rubber material which may effect some analysis although viton packers are
feas i bIe.
Gas pressure lift systems are useful in many instances. They are usually
light, easy to install, and can be powered by several different pressure
systems, usually compressed nitrogen or air. The effect of the contact between
the pressure gas and the groundwater usually results in changes in the
dissolved gas content.5As a result pH, conductivity, or other analysis used
to determine purge completion must be conducted down hole.
Peristaltic pumps are widely used for purging of wells with water levels
close to the surface (less than 8 meters). They are reasonably portable,
light, and easily adaptable to ground level monitoring of purge indicator
parameters by attaching a flow-through cell. These pumps require a minimum of
down hole equipment and can easily be cleaned in the field; or the entire
tubing assembly can be changed for each well.
Several manufacturers are marketing submersible pumps specifically
designed for groundwater monitoring. They are generally capable of fitting
down 2-inch ID wells. Most of these pumps have effective depth limitations of
less than 150 feet. Although some can operate to depths in excess of 300 ft.,
they usually have substantially reduced discharge flows and significant power
consumption. All electrically powered equipment should be checked for
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electrical safety certification (UL, FM, NFPA, NEC). Appendix F discusses the
various certifications in detail.
Three basic designs are currently available:
Eductors--A pump is used to circulate water through a venturi, the
resultant pressure drop across the venturi is used to draw sample
into the recircuI ating stream. A split stream is drawn off the
recircuI ating stream equal to the flow at the intake. These systems
require priming water and must be run long enough to insure complete
removal of the priming water from the recircuI ation loop. They
readily fit into a 2-inch diameter well and will recover samples
from as deep as 100 ft or 50 ft in a 1-1/2 inch ID well.
Submersible Motor--A small submersible electric motor is used to
drive a common stator/rotor pump. They will fit inside a 2-inch ID
well and operate at depths to approximately 150 ft. The discharge
flow varies with depth" from 1.2 gpm at 10 ft to 0.6 gpm at 125 ft.
Bladder Compress ion--A flexible bladder with a check valve at either
end is suspended inside a rigid chamber. Hydrostatic pressure
forces water into the bladder. The chamber is then pressurized which
squeezes the bladder and forces the water out the other check valve
and into the discharge tubing. This cycle is then repeated until the
sample is recovered.
The pump is operated by a compressed air source, either bottled gas
or a small DC powered compressor. Pumps are available that can
sample from depths of 250 ft. Flow rates vary with models but range
from about 2.0 gpm at 25 ft to 0.5 gpm at 150 ft. (At least one
model is capable of 0.78 gpm at 250 ft.)
Once the well has been sufficiently purged, the actual sampling should
begin as soon as the water level begins to approach its pre-purge level.
Sampling for volatile organics may begin even sooner, before substantial
volatilization begins. If recovery is very slow, it may be necessary to wait
several hours or even until the following day before sufficient volume is
available for all the necessary analyses. In this instance a volatile
organics sample set may be collected soon after completion of the purging
process and a second set with the remaining samples. When a pump is used for
sample collection, its rate should be controlled, if possible to closely match
the transmissivity of the formation. Excessive draw down of the well during
sampling may result in nonrepresentative samples due to changes in groundwater
flow.9
Bailers are probably the simplest means of collecting groundwater samples.
They result in a minimum of sample disturbance if carefully handled. They can
be constructed of noncontaminating materials, and their low relative cost makes
the use of a separate device for each well practical, thus eliminating in-field
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cleaning and cross contamination. Peristaltic pumps can be used for sampling
in most shallow wells. They require a minimum of down-hole equipment and
cross contamination can be eliminated b replacement of the suction tubing
between wells. G i bb10 as well as NCASTfound little difference between
samples withdrawn by a peristaltic pump and those taken by a bailer. These
pumps however may not be suitable for the collection of volatile organics due
to possible gas stripping; therefore, their use should be supplemented by a
bailer when sampling includes volatile organic species.
The use of submersible pumps as described previously for sample collection
is possible provided they are constructed of suitably noncontaminating
materials. They can operate at depths beyond the capabilities of peristaltic
pumps and at which depths bailing becomes tedious. The chief drawback,
however, is the difficulty of avoiding cross contamination between wells.
These systems are generally too expensive to allow for several separate units.
Though some units can be easily disassembled and allow for replacement of most
sample contacted surfaces, field decontamination still may be difficult and
should properly require solvents that may lead to sample contamination. Their
use therefore, in multiple well programs, should be carefully considered
aga inst ba i lers.
In general, gas pressure displacement systems where gas interfaces with
the liquid should not be used for sample collection as they have been shown to
cause considerable changes in the groundwater character.10
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3.4.1 METHOD III-7: PURGING WITH A PERISTALTIC PUMP
Discussion
The peristaltic pump as described in the surface water sampling section
Method III-3 can be implemented for the presample purging of groundwater
monitor we I Is.
Uses
The use of a peristaltic pump for well purging is particularly
advantageous since the same systemcan later be used for sample collection
(see Method 111-10). The application, however, is limited to wells with a
depth of less than approximately 8 meters, due to the limited lift
capabilities of peristaltic action
Procedures for Use
Using clean equipment, sound well for total depth and water level,
then-calculate the fluid volume in the casing ("casing volume").
Determine depth from casing top to mid-point of screen or well
section open to aquifer. (Consult drillers log, or sound for
bottom.)
If depth to mid-point of screen is in excess of 8 meters, choose
alternate system.
Lower intake into the well to a short distance below the water level
and begin water removal. Collect or dispuse of purged water in an
acceptable manner. Lower suction intake, as required, to maintain
submergence.
Measure rate of discharge frequently. A bucket and stopwatch are
most commonly used.
Purge a minimum of four casing volumes or until discharge, pH,
temperature, or conductivity stabilize. See discussion on well
purging in Section 3.4, Groundwater.
After pumping, monitor water level recovery. Recovery rate may be
useful in determining sample rate.
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3.4.2 METHOD III-8: PURGING WITH A GAS PRESSURE DISPLACEMENT SYSTEM
Discussion
A pressure displacement system consists of a chamber equipped with a gas
inlet line, a water discharge line and two check valves (see Figure 3-7).
When the chamber is lowered into the casing, water floods it from the bottom
through the check valve. Once full, a gas (i.e., nitrogen or air) is forced
into the top of the chamber sufficient to result in the upward displacement
of the water out the discharge tube. The check valve in the bottom prevents
water from being forced back into the casing, and the upper check valve
prevents water from flowing back into the chamber when the gas pressure is
released. This cycle can be repeated as necessary until purging is complete.
Uses
The pressure lift system is particularly useful when the well depth is
beyond the capability of a peristaltic pump. The water is displaced up the
discharge tube by the increased gas pressure above the water level. The
potential for increased gas diffusion into the water makes this system
unsuitable for sampling for volatile organic or most pH critical parameters.10
Procedures for Use
1, Using clean noncontaminating equipment, i.e., an electronic level
indicator (avoid indicating pastes) determine the water level in the
well, then calculate the fluid volume in the casing.
2, Determine depth to midpoint of screen or well section open to aquifer
(consuIt dri Ilers log).
3, Lower displacement chamber until top is just below water level.
4, Attach gas supply line to pressure adjustment valve on cap.
5, Gradually increase gas pressure to maintain discharge flow rate.
6, Measure rate of discharge frequently. A bucket and stopwatch are
usuaIly sufficient.
7. Purge a minimum of four casing volumes or until discharge
characteristics stabilize (see discussion on well purging in Section
3.4, Groundwater).
8. After pumping, monitor water level recovery. Recovery rate may be
useful in determining sample rate.
U. S. Environmental Protection Agency. "Procedures Manual for Ground Water
Monitoring at Solid Waste Disposal Facilities," EPA-530/SW-611, August 1977
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Section 3.4.2
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FROM COMPRESSED
GAS CYLINDER OR
AIR PUMP
QUICK HOSE COUPLER
NEEDLE VALVE
PRESSURE GAUGE
DISCHARGE
SAMPLE LINE
TO WASTE
BOTTLE
DISCHARGE SAMPLE
LINE
CHECK VALVE
SAMPLER BODY
CHECK VALVE
WELL CASING
Source: Reference 6.
Figure 3-7. Gas pressure displacement system.
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3.4.3 METHOD III-9: SAMPLING MONITOR WELLS WITH A BUCKET TYPE BAILER
Discussion
Bucket type bailers are tall narrow buckets equipped with a check valve
on the bottom. This valve allows water to enter from the bottom as the bailer
is lowered, then prevents its release as the bailer is raised (see Figure 3-8).
Top filling bailers are also available and may be useful for well purging but
generally result in increased sample turbulence and are not recommended for
sample acquisition.
Uses
This device is particularly useful when samples must be recovered from
depths greater than the range (or capability) of suction lift pumps, when
volatile stripping is of concern, or when well casing diameters are too narrow
to accept submersible pumps. It is the method of choice for the collection of
samples which are susceptible to volatile component stripping or degradation
due to the aeration associated with most other recovery systems. Samples can
be recovered with a minimum of aeration if care is taken to gradually lower the
bailer until it contacts the water surface and is then allowed to sink as it
fills. Teflon is generally the best construction material but other materials
(PVC, stainless steel, etc.) are acceptable if compatible with designated
sample analysis. The primary disadvantages of bailers are their limited sample
volume and inability to collect discrete samples from a depth below the water
surface.
Procedures for Use
1. Using clean, noncontaminating equipment, i.e., an electronic level
indicator (avoid indicating paste), determine the water level in the
well, then calculate the fluid volume in the casing.
2, Purge well as per Methods III-7 or III-8.
3, Attach precleaned bailer to cable or line for lowering.
4, Lower bailer slowly until it contacts water surface.
5, Allow bailer to sink and fill with a minimum of surface disturbance.
6, Slowly raise bailer to surface. Do not allow bailer line to contact
ground.
7. Tip bailer to allow slow discharge from top to flow gently down the
side of the sample bottle with minimum entry turbulence.
8, Repeat steps 2-5 as needed to acquire sufficient volume.
9, Select sample bottles and preserve the sample, if necessary,
according to the guidelines in Appendix A.
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STAINLESS WIRE
CABLE
l-l/4"o.D.x l" 1.0. TEFLON
EXTRUDED TUBING,
18 TO 36"LONG
3/4 DIAMETER
GLASS OR TEFLON
JS- I DIAMETER TEFLON
EXTRUDED ROD
"5/16" DIAMETER
HOLE
Figure 3-8. Teflon bailer.
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Section 3.4.3
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10, Check that a Teflon-liner is present in cap if required. Secure the cap
tightly.
11. Label the sample bottle with an appropriate tag. Be sure to complete the
tag with all necessary information. Record the information in the field
logbook and complete all chain-of-custody documents.
12, Thoroughly decontaminate the bailer after each use according to specific
laboratory instructions, or the general guidelines in Appendix E. In some
cases, especially where trace analysis is desired, it may be prudent to
use a separate bailer for each well.
Sources
Dun lap, W. J., McNabb, J. F., Sea If, M. R. and Crosby, R. L., "Sampling for
Organic Chemicals and Microorganism in the Subsurface. "EPA-600/2-77-176,
August 1977.
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3.4.4 METHOD 111-10: SAMPLING MONITOR WELLS WITH A PERISTALTIC PUMP
Discussion
A pump system is considerably advantageous when analytical requirements
demand sample volumes in excess of several liters. The major drawback of a
pump system is the potential for increased volatile component stripping as a
result of the required lift vacuum. Samples for volatile organic analysis
should be collected with a bailer as described in Method III-9 and should
precede any sample collection which may further disturb the well bore content.
Uses
The peristaltic pump system can be used for monitor well sampling whenever
the lift requirements do not exceed 8 meters (for deeper wells see Method
111-11). It becomes particularly important to use a heavy wall tubing in this
application in order to prevent tubing collapse under the high vacuums needed
for lifting from depth.
Procedures for Use
1. Using clean, noncontaminating equipment, i.e., an electronic level
indicator (avoid indicating paste), determine the water level in the
well, then calculate the fluid volume in the casing.
2, Purge well as per Methods
I-7 or
3, If soundings show sufficient level of recovery, prepare pump system.
If insufficient recovery is noted allow additional time to collect
samples on a periodic schedule which will allow recovery between
samp I ings.
4, Collect volatile organic analysis samples if required with bucket
type bai ler (Method I I I -9) .
5, Install clean medical grade silicon tubing in peristaltic pump head.
6, Attach pump to required length of prec leaned Teflon suction line and
lower to midpoint of well screen if known or slightly below existing
water level .
7, Consider the first liter of liquid collected as a system purge/rinse.
NOTE : If well yield is insufficient for required analysis this purge
volume may be suitable for some less critical analysis.
8, Fill necessary sample bottles by allowing pump discharge to flow
gently down the side of bottle with minimal entry turbulence. Cap
each bottle as f i I led.
9, Select sample bottles and preserve the sample if necessary as per
guidelines in Appendix A.
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10, Check that a Teflon-liner is present in cap if required. Secure the
cap tightly.
11. Label the sample bottle with an appropriate tag. Be sure to complete
the tag with all necessary information. Complete chain-of-custody
documents and field logbook.
12. Allow system to drain then disassemble. Return tubing to lab for
decontamination. See Appendix E for general decontamination
procedures.
Sources
Dun lap, W. J., McNabb, J. F., Scalf, M. R. and Crosby, R. L. "Sampling for
Organic Chemicals and Microorganisms in the Subsurface," EPA-600/2-77-176,
August 1977.
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3.4.5 METHOD 111-11: SAMPLING MONITOR WELLS WITH A SUBMERSIBLE PUMP
Discussion
Several types of submersible pumps are available for groundwater
monitoring and offer considerable advantages over other systems. They are
able to operate from depths beyond the capabilities of peristaltic pumps and
save significant time and effort relative to hand bailing. Further, if
constructed of suitable materials and properly used, they can both purge and
adequately sample the well.
Submersible pumps generally use one of two types of power supplies, either
electric or compressed gas. Electric powered pumps generally run off a 12 VDC
rechargeable battery from an automotive electrical system. Those units powered
by compressed gas normally use a small electric compressor which also needs 12
VDC power. They may also utilize compressed gas from bottles or even high
performance hand pumps.
These pumps are generally constructed of "more or less" noncontaminating
materials "suitable for Priority Pollutant Sampling". They often contain
plastics, rubber or metal parts which may contribute or otherwise effect the
analysis of samples for certain trace components. Investigations requiring
samples for a wide range of trace analysis may preclude their use for sample
acquisition; however, they may still be useful for purging. In any case, when
doubt remains, bailers are the best choice for actual sample acquisition.
Procedures for Use
1. Using clean, noncontaminating equipment, i.e., an electronic level
indicator (avoid indicating paste or chalk), determine the water
level in the well, then calculate the fluid volume in the casing
2, Lower the precleaned pump to just below the water level and begin
pumping. Collect or dispose of purged water in an acceptable manner.
Lower the pump as required to maintain submergence.
3, Measure rate of discharge frequently. A bucket and stopwatch are
commonly used.
4, Purge a minimum of four casing volumes or until discharge pH,
conductivity, or temperature stabilize. See discussion on well
purging in Section 3.4, Groundwater. (Note: If the pump is
constructed of materials compatible with the required sample
analysis and if the well has recovered sufficiently (resound water
level) sample acquisition can proceed as follows. It should be
cautioned that all down hole and potentially wetted surfaces must
also be noncontaminating/noncontribut ing. This includes power and
suspension cables and compressed gas or sample tubing.)
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Fill necessary sample bottles by allowing pump discharge to flow
gently down the side of bottle with minimal entry turbulence. Cap
each bottle as fi I led.
Select appropriate sample bottles and preserve the sample if
necessary as per guidelines in Appendix A.
Check that a Teflon-liner is present in cap if required. Secure the
cap tightly.
Label the sample bottle with an appropriate tag. Be sure to complete
the tag with all necessary information. Complete chain-of-custody
documents and field logbook.
Allow system to drain then disassemble. Return tubing to lab for
decontamination. See Appendix E for general decontamination
procedures.
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Section 3.5
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3.5 REFERENCES
1. United States Department of the Interior National Handbook of
Recommended Methods for Water--Data Acquisition. Reston, Virginia.
1977.
2, deVera, E. R., B. P. Simmons, N. D. Stephen, and D. L. Storm.
Samplers and Sampling Procedures for Hazardous Waste Streams.
EPA-600/2-80-018.
3, Instrument Specialties Company, Instruction Manual, Model 2100
Wastewater Sampler. Lincoln, Nebraska. January 1980.
4, National Council of the Paper Industry for Air and Stream
Improvement, Inc. A Guide to Groundwater Sampling. Technical
Bulletin No. 362. Madison, New York. January 1982.
5, McNabb, J. F. and G. E. Ma I lord. Introduction to Subsurface
Microbiology and Sampling Problems. Presented at the American
Society for Microbiology Annual Meeting, Miami Beach, Florida. May
1980.
6. Scalf, M. J., J. F. McNabb, W. Dunlap, R. Crosby, and J. Fryberger.
Manual for Groundwater Sampling Procedures. R. S. Kerr Environmental
Research Laboratory, Office of Research and Development. Ada, OK.
1980.
7, Sisk, S. W. NEIC Manual for Ground/Subsurface Investigations at
Hazardous Waste Sites. EPA-330/9-81-002. 1981.
8, Gibb, J.P., R. M. Schuller, and R. A. Griffin. Monitoring Well
Sampling and Preservation Techniques. EPA-600/9-80-010. March 1980.
9, U.S. Environmental Protection Agency. Procedures Manual for
Groundwater Monitoring at Solid Waste Disposal Facilities.
EPA-530/SW-611 . August 1977.
10. Gibb, J. P., R. M. Schuller, and R. A. Griffin. Collection of
Representative Water Quality Data From Monitoring Wells in Land
Disposal.
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SECTION 4.0
GASES, VAPORS, AND AEROSOLS
4.1 GENERAL
Air monitoring at hazardous waste sites and environmental spills can be
quite useful as an indicator of potential safety problems and as a means of
screening for the presence of possible airborne contaminants. Monitoring is
also important as a means of determining the specific identity and
concentration of airborne toxic and hazardous pollutants onsite and the extent
of their migration offsite for both worker and public health risk assessments.
For the purpose of this document, sampling for gases, vapors and aerosols at
hazardous waste sites and environmental spills falls into three general
categories: the ambient atmosphere, soil gases, and container headspace gases.
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4.2 AMBIENT
Ambient concentrations of airborne contaminants are greatly affected by
the topography and meteorology of the surrounding area, and the investigator
must be cognizant of this when choosing monitoring methods and equipment.
Besides the obvious effects of temperature, wind, and precipitation in
relation to dispersion and deposition of atmospheric pollutants, heat and
sunlight can dramatically increase rates of volatilization, and cold and calm
may cause stagnant conditions to prevail tending to reduce migration and to
concentrate pollutants in low-lying areas. Accurate detection of atmospheric
pollutants must take into account these and other factors if a successful
sampling effort is desired.
Of major importance when discussing the sampling of ambient atmospheres
is the use of portable analytical instrumentation. In addition to being
portable, these devices need to be rugged and easy to operate and need to
provide real time data in order to best meet the requirements inherent to
field applications. They must also be proven safe when used in hazardous
waste environments. Electrical devices and instruments which use flame or
combustion principles must be of a type that eliminate the possibility of
igniting combustible atmospheres. All instruments used should be "approved"
or "certified" by Underwriters Laboratory (UL) or Factory Mutual Systems (FM)
according to provisions set forth by the National Electrical Code (NEC). A
detailed discussion of the various electrical product certification programs
is presented in Appendix F. In addition, this appendix contains an
explanation of the various atmosphere Classes, Divisions, and Groups for which
these devices are approved.
In order to insure safe operation, the user must also become familiar
with the detailed operation and maintenance procedures found only in the
operating manual of each specific instrument. The investigator should keep
in mind that the procedures outlined here are necessarily general and intended
only to supplement the instrument operating manual. Investigators must also
familiarize themselves with the limitations of each instrument. Inability
to detect certain compounds, insensitivity (e.g., contaminants in the solid
phase), slow response time, pump rate capacity, etc. are all factors which may
affect the safety of the operator and/or quality of the data.
Field instrumentation is invaluable during initial site surveys for
assessing the potential hazards that exist. Information of this nature is
needed in order to determine the degree of protection required for personnel
or to provide direction for further quantification of specific parameters.
Instruments such as portable oxygen indicators and combustible gas
detectors would be the instruments of choice when a general safety assessment
of an unknown atmosphere is necessary. Such atmospheres present many hazards
including oxygen deficiency, explosivity, flammabi I ity, etc., and data
obtained with these instruments can be used by the onsite safety officer to
generally assess the presence of these dangers and dictate precautionary
measures to be taken. They can be used to screen pockets or depressions in
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the land contour, areas in close proximity to drums or spills, or closed in,
unventi lated rooms which may not have enough oxygen to support life or which
allow combustible vapors to concentrate.
Other instruments that may be required for evaluating the hazard
potential of ambient or workplace atmospheres are those which utilize flame
ionization (FID) and photoionization (PID) detectors. These detectors are
important due to the increased levels of sensitivity they can provide (for
specific compound classes) and when used in conjunction with chromatographic
columns, can specifically characterize and/or identify hazardous materials at
spi I Is or dump sites.
The Century OVA and AID Model 550 represent a type of instrument which
uses a flame ionization detector. In its simplest form this type is used to
determine the presence of gaseous and/or vapor phase hydrocarbons. These
instruments responded to most gaseous/vapor phase organics present. The readings
are referenced to a single component standard gas (usually methane). The
response of such instruments is often termed "total hydrocarbons;" however,
this is misleading since not all hydrocarbons are detected, specifically,
important particulate hydrocarbons (i.e., pesticides and polynuclear aromatics),
and polychlorinated biphenyls. In addition, the response to mixtures of vapor
phase hydrocarbons depends upon the ratios and the types of organic compounds
present and cannot be related to a specific vapor concentration. FIDs do,
nonetheless, provide a useful and reliable tool for general assessment
purposes.
Photo ionization analyzers such as the portable HNU Model P1-101 are also
capable of detecting the presence of a wide variety of chemical species, both
organic and inorganic. As with FID's, photo ionization detectors suffer
similar limitations of detector response to component mixtures. The inability
to respond to certain compounds must be recognized; however, PID's can provide
important information for evaluation purposes.
As stated previously, the usefulness of both portable FID's and PID's can
be expanded when used in conjunction with gas chromatography. The Century
units offer a chromatography option which, when used properly, can be quite a
valuable tool for aiding in specific compound identification. At present, the
HNU P1-101 is not available with a chromatography option; however Spittler and
Oi1 report success with a portable photo ionization detector/gas chromatography
(Photovac 10A10, Thornhill, Ontario) capable of sensitivity in the 0.1 to 10
ppb range. In all cases it should be realized that chromatography can be
quite complex and demands the skills of an experienced operator to obtain
valid and meaningful results.
Additional useful instruments and devices include those adapted from
industrial hygiene practices and/or techniques. These include stain detector
tubes and personnel collection devices. Detection by these methods is the
most specific of all of the devices thus far described. These methods are
therefore extremely useful for compound identification and quantification.
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Stain detector tubes such as manufactured by National Drager,
Matheson-Kitagawa, Bendix Corporation, and MSA provide an immediate indicator
of a specific chemical or species of interest. They are somewhat limited due
to small sample volume, interferences, degree of accuracy, operator judgement,
etc.; however, they are valuable as a quick, relatively simple, direct-read ing
method of determining specific gas concentrations.
Collection devices such as solid sorbents, chemical absorbing solutions
and filters are the most accurate of the methods used for properly identifying
and quantifying species of interest. Use of these methods requires adherence
to very specific procedures and conditions of the type found in the "NIOSH
Manual of Analytical Methods,"2 EPA Federal Reference Methods, or specific
papers documenting procedures and characteristics of sorbent resins.
Collected samples are subsequently analyzed at an offsite analytical
laboratory that usually yields an analytical precision and accuracy presently
unavailable in most field applications.
It should be noted, at this point, that ambient monitoring, within the
context of this section, deals with area monitoring and not personnel
monitoring. Although ambient methods can provide information on the types of
contaminants present and the relative magnitude of contamination, it is not a
substitute for personnel monitoring when worker exposure is the prime concern.
In such cases, NIOSH methodologies should be consulted and appropriate methods
chosen dependent upon specific monitoring requirements.
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4.2.1 METHOD IV-1 : DETERMINING OXYGEN CONTENT IN AMBIENT AND WORKPLACE
ENVIRONMENTS WITH A PORTABLE OXYGEN MONITOR
Discussion
A portable oxygen monitor has three principle components for operation:
the airflow system, the oxygen sensing device, and the microamp meter.
Typically the air is drawn through the oxygen sensor with a built-in pump
or aspirator bulb, although some instruments use passive cells. The
sensor indicates the oxygen content and the information is translated
electrochemicaIly to the meter.
Most monitors have meters which indicate the oxygen content from 0-25
percent. There are also oxygen monitors available which indicate
concentrations on scales from 0-5 percent and 0-100 percent. The most useful
for ambient measurements is the 0-25 percent oxygen content readout. Many
instruments also have alarm modes which can be set to activate at a specified
oxygen concentration.
Uses
Portable oxygen monitors are invaluable when initially responding to
hazardous material spills or waste site situations. They are useful in
screening depressions in the land, unventi lated rooms, or other areas that may
not contain enough oxygen to support life. When used properly the portable
oxygen monitor will indicate the percent oxygen in the test atmosphere.
Normal oxygen concentration required for respiration is 20.9 percent.
Procedures for Use
1. Make sure instrument is clean and serviceable, especially sample
lines and detector surfaces.
2, Consult records on instrument maintenance to determine if detector
solution should be changed. Some instruments will need this service
after as little as 1-2 weeks of use.
3, Check battery charge level. If in doubt, charge battery as detailed
in operating manual. Some units have charge level indicators while
others have alarms that will indicate a low charge.
4, Verify that sample pump is operable (if so equipped) when analyzer is
on.
5, Turn instrument on and, using calibration knob on instrument,
calibrate against fresh air (20.9 percent OJ by aligning meter
needle at 20.9 percent.
6, If unit is equipped with alarm mode, set alarm at desired level.
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Section 4.2.1
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7, A quick field check can be accomplished by exhaling into the sensor,
this should cause a definite drop in 02 readings and activate any
alarms. Allow for instrument warmup, if necessary, before entering
site to take readings.
8, Position intake assembly or sensor in close proximity to area in
question to get accurate reading.
9, If alarm occurs, personnel should evacuate area, unless equipped with
supplied air equipment suitable for use in an IDLH atmosphere.
10, Some important factors to keep in mind during use are:
Slow sweeping motions may assist in the prevention of bypassing
problem areas.
Operation of instrument in temperatures outside of manufacturer
specified operating range may compromise accuracy of readings
or damage unit. The instrument should always be calibrated at
the temperature of intended use.
. Presence of known or unknown interfering gases, especially
oxidants, can affect readings (for example the Edmont Model
60-400 Oxygen Monitor has interferences of the following gases
in concentrations greater than 0.25 percent or 2500 ppm:
S02, fluorine, chlorine, bromide, iodines and nitrogen oxides).
See the operating manual for unit being used.
. The oxygen detector can also be poisoned (decrease in
sensitivity) by exposure to various gases. Some detectors are
poisoned by concentration of mercaptans and hydrogen sulfide
greater than or equal to 1 percent. See operating manual for
unit being used.
. When relying on alarm mode for warnings of oxygen deficient
atmospheres, a manual check of the alarm function at regular
intervals is recommended.
. Wherever applicable, protect instrument with a disposable cover
to prevent contamination.
. Most units will have rechargeable battery packs that provide
continuous operation for 8-12 hours. Recharging batteries
prior to expiration of the specified interval will insure
operation while on a site.
More than any other factor, effective utilization of unit
requires operator with full understanding of operating
principles and procedures for the specific instrument in use.
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Section 4.2.1
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Sources
Edmont Model 60-400 Combustible Gas/Oxygen Monitor Instruction Manual.
Manufactured by Energetic Science, Elmsford, NY 10523.
U.S. Environmental Protection Agency. "Hazardous Materials Response
Operations Training Manual." National Training and Operational Center,
Cincinnati, OH.
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Section 4.2.2
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4.2.2 METHOD IV-2: DETERMINATION OF COMBUSTIBLE GAS LEVELS USING A
PORTABLE COMBUSTIBLE GAS INDICATOR
Discussion
A combustible gas indicator consists of three primary components: the
sensor (hotwire, catalytic, solid state, etc.), signal processor and readout
display. Sample is introduced to the sensor either by diffusion into a
passive sensor or by pumping. The sensor produces a signal which is processed
and displayed as the ratio of the combustible gas present to the total
required to reach the lower explosion limit (LEL).
The lower explosive limit (also LFL, lower flammability limit) is
defined as the lowest concentration of gas or vapor in air which can be
ignited by an ignition source and cause an explosion or flame propagation.
Conversely, the upper explosive limit or UEL (also UFL, upper flammability
limit) is the concentration of gas in air above which there is insufficient
oxygen available to support combustion, and an explosion is unlikely. A
flame, however, may burn at the gas-air interface or, should additional air
enter the mixture, a very explosive atmosphere may develop. In general, the
instruments respond in the following manner.
The meter indicates 0.5 LEL (50 percent). This means that 50
percent of the concentration of combustible gas needed to reach
an unstable combustible situation is present. If the LEL of the
gas is 5 percent in air, then the instrument indicates a 2.5
percent mixture is present.
The meter needle stays above 1.0 LEL (100 percent). This means that
the concentration of combustible gas is greater than the LEL and
less than the UEL and, therefore, immediately combustible and
explosive.
The meter needle rises above the 1.0 (100 percent) mark and then
returns to zero. This response indicates the ambient atmosphere has
a combustible gas concentration greater than the UEL.
Of the many instruments commercially available for detecting combustible
or explosive gas, some are not certified safe for operation in the atmospheres
they can detect. It is important to use only those monitors that are
certified safe for use in atmospheres greater than 25 percent of the LEL.
Appendix F discusses the electrical product certification programs and details
the various atmosphere divisions, classes and groups for which these products
are tested.
Some combustible gas monitors provide readouts in units of percent LEL,
some in percent combustible gases by volume, and some have scales for both.
Many situations may occur where the types of combustible gases to be
encountered are unknown. In such instances the more explosive the calibration
gas (the lower the LEL) the more sensitive the indication of explosivity and
thus the greater the margin of safety. The operator should be familiar with
4-8
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Section 4.2.2
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the LEL concentrations for specific gases to effectively use instruments that
provide data in percent combustible (by volume) only.
Although monitors can be purchased that are factory calibrated using
gases such as butane, pentane, natural gas, or petroleum vapors, methane
calibration is the most common. The LEL of methane is 5 percent by volume in
air, therefore, an air mixture containing 5 percent methane will be read as
100 percent LEL and will be explosive if a source of ignition is present.
When combustible gases other than methane are sampled, the relative response
of the detector for these other gases must be considered. Recal ibrat ion to
other gases may be possible; see manufacturers recommendations. The relative
sensitivity of the detector and the differences in LEL for different gases
will produce varying meter responses equal concentrations of different gases.
Actual correlation equations that will convert the percent LEL (based on
methane) read by the unit to a percent LEL for another combustible gas can
usually be found in the operating manual.
Many units also have alarm systems which can be adjusted for various
LEL's and several are available that incorporate oxygen analyzers.
Uses
In general, combustible gas detectors are used to determine the potential
for combustion or explosion of unknown atmospheres. These instruments, in
combination with oxygen detectors and radiation survey instrumentation, should
be the first monitors used when entering a hazardous area. In this sense they
provide a general indication of the degree of immediate hazard to personnel
and can be used to assist the safety officer in making decisions on levels of
protection required at the site. However, they provide little or no information
about the presence of compounds hazardous or toxic at trace level concentrations.
Procedure for Use
1. Make sure instrument is clean and serviceable, especially sample
lines and detector surfaces.
2, Check battery charge level. If in doubt, charge battery as
described in operating manual. Some units have charge level meters,
while others have only low charge alarms.
3, Turn unit to ON position, and allow instrument sufficient warmup
time.
4. Verify that sample pump is operable (if so equipped) when analyzer
is ON.
5, With the intake assembly in combustible gas-free ambient air, zero
the meter by rotating the zero control until the meter reads 0
percent LEL.
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Section 4.2.2
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6, Calibrate unit against known concentration of a calibration gas by
rotating the calibration control (span or gain) until the meter
reads the same concentration as the known standard. For those
instruments with internal or nonadjustable span, a calibration curve
should be prepared, using concentrations in the range expected to be
encountered.
7, If necessary, adjust alarm setting to appropriate combustibility
sett i ng.
8, Position intake assembly or cell in close proximity to area in
question to get accurate reading.
9, If alarm occurs, or if readings reach the action levels designated
in the safety plan, personnel should evacuate area.
10, If instrument malfunction occurs, personnel should evacuate area.
11. Some important factors to keep in mind during use are:
Slow sweeping motions of intake or cell assembly will help
assure that problem atmospheres are not bypassed. Cover an
area from floor (ground) to ceiling, or above breathing zone.
Operation of unit in temperatures outside of recommended
operating range may compromise accuracy of readings or damage
the instrument.
Platinum filament detectors may be poisoned (reduced in
sensitivity) by gases such as leaded gasoline vapors
(tetraethyl lead), sulfur compounds (mercaptans and hydrogen
sulfide) and silicon compounds.
Many combustible gas detectors are not designed for use in
oxygen-enriched or depleted atmospheres. If this condition is
encountered or suspected, personnel should evacuate the area.
Specially designed units are available for operation in such
atmospheres.
An oxygen detector should always be used in conjunction with
explosimeters.
Accurate data depends on regular calibration and battery
charging. See operating manual.
More than any other factor, effective utilization of unit
requires operator with full understanding of operating
principles and procedures for the specific instrument in use.
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Section 4.2.2
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Sources
Edmont Model 60-400 Combustible Gas/Oxygen Monitor Instruction Manual.
Manufactured by Energetic Science, Elmsford, NY 10523.
U.S. Environmental Protection Agency. "Hazardous Materials Incident
Response Operators Training Manual." National Training and Operationa
Training Center, Cincinnati, Ohio.
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4.2.3 METHOD IV-3: MONITORING ORGANIC VAPORS USING A PORTABLE
FLAME IONIZATION DETECTOR
Discussion
A flame ionization detector (FID) will respond to most organic vapors as
they form positively charged ions when combusted in a hydrogen flame. The
magnitude of the response is a function of the detector sensitivity and the
ionization properties of the particular compound as well as its concentration.
As a result, this signal must be compared to that generated by calibration
with a known concentration of a standard gas. The sample concentration is
then reported as the ppm equivalent of the calibration compound. Most units
are calibrated with a known concentration of methane; however, almost any
gaseous hydrocarbon that produces a response can be used. Many models also
have built-in calibration circuits which can insure that the electronic
response to a known signal remains constant.
Some models can be equipped with an option that provides chromatographic
separation of the sample gas constituents. This permits a tentative
qualification and quantification to be made of the resultant peaks which
have retention times equal to those of known standards. This option requires
the use of a chart recorder for recording the peak areas and retention times,
and in such a mode, prevents the instrument from providing a continuous
readout. Use of a chromatographic option also requires additional expertise
if reliable, consistent results are desired.
Most portable FID's rely on the sample gas to supply the combustion air
to the detector flame, so they are designed to operate in ambient atmospheres
with relatively normal oxygen concentrations (21 percent). This design
precludes the sampling of process vents, poorly ventilated or sealed containers,
or any sample gas hydrocarbon concentration sufficient to reduce the available
oxygen or otherwise saturate the detector. In such instances adaptations
are usually aval I able to supply a source of oxygen from a compressed gas bottle
or introduce the gas through a dilution system with a known (calibrated)
di lution factor.
Uses
A portable FID is useful as a general screening tool to detect the
presence of most organic vapors. It will not, however, respond to particulate
hydrocarbons such as pesticides, PNAs, and PCBs. It can be used to detect
pockets of gaseous hydrocarbons in depressions or confined spaces, to screen
drums or other containers for the presence of entrapped vapors, or generally
to assess an area for the presence of elevated levels of vapor phase organics.
Procedure for Use
The procedures presented in this section are intended to apply to any
portable FID; therefore, detailed operating instructions must be obtained
from the operating manual of the specific unit to be used.
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Section 4.2.3
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1. Check battery charge level indicator; if in doubt, recharge battery
as described in manual.
2, Turn instrument on and allow adequate warmup time.
3, If equipped with internal calibration capability, perform instrument
calibration. Perform zero and other calibration procedures as
described in operating manual.
4, If equipped with an alarm mode, set alarm at desired concentration.
5, Turn on pump and check for leaks by covering sample inlet and
observing rotameter. Indicator ball should drop to zero level.
6, With pump operating, open hydrogen gas storage tank valve and open
supply regulator to allow fuel gas flow to detector chamber.
7, Depress igniter switch, observe indicator needle for positive
response and listen for a "pop." If flame fails to light, depress
igniter switch again.
8, Once detector flame is lit, unit is ready for use.
9, If calibration to a specific hydrocarbon species is desired,
complete this procedure according to the manufacturers instructions.
10, Hold sample probe in close proximity to area in question as low
sample rate allows for only very localized readings.
11. Slow sweeping motion will help prevent the bypassing of problem
areas. Make sure batteries are recharged within time frame
specified in operator manual. Usual length of operating time
between charges is 8-12 hours.
12. Some units have alarms that signal operator if detector flame goes
out. If this alarm sounds, evacuate all personnel and relight flame
in known safe area then reenter site.
13. Monitor fuel and/or combustion air supply gauges regularly to insure
sufficient gas supplies.
14, High background readings after prolonged use may indicate sample
probe and/or in-line filters (in front of detector) need to be
cleaned. Use of pipe cleaners or clean air blown backwards through
filters is adequate. Do not use organic solvents as detector will
respond to solvent as well.
15. Representative readings will also depend on performance of routine
maintenance as described in detail in operating manual. Also, since
unit contains pressurized gas supplies, perform leak check procedures
regularly, as leaking hydrogen gas is explosive.
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Sect i on 4.2.3
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16. As with any field instrument, accurate results depend on the operator
being completely familiar with the operator's manual for the
particular unit.
17. Concentrations beyond the greatest scale factor of the instrument or
in excess of 30 percent (0.3) LEL of the sample component require
system modification. Similar modification may be necessary for
sampling in oxygen-deficient atmospheres. This usually entails
increasing the combustion air to the detector by sample dilution or
by an independent air supply. A dilution system is simply the
apparatus required to supply a filtered, controlled air supply for
analyzers that use the sample gas stream as the source of combustion
air. A dilution system can, by selection of various critical
orifices, dilute a gas stream by ratios up to 100:1.
18. Always be sure that carrier gas flow (usually sample gas) is
initiated prior to lighting the detector flame.
Sources
Analabs, A Unit of Foxboro Analytical. "Operating and Service Manual for
Century Systems' Portable Organic Vapor Analyzer (OVA) Model OVA-108 and
Optional Accessories, Revision C," North Haven, Connecticut.
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4.2.4 METHOD IV-4: MONITORING TOXIC GASES AND VAPORS USING
A PHOTO I ON IZATI ON DETECTION
Discussion
This method is designed to detect, measure and record real-time levels of
many organic and inorganic vapors in air. A photoionization detector (PID)
will respond to most vaporous compounds in air that have an ion izat ion
potential less than or equal to that supplied by the ionizing source in the
detector, an ultraviolet lamp. The magnitude of this response is a function
of the detector sensitivity and the concentration and ionization properties of
the individual compound. Though it can be calibrated to a particular compound,
the instrument cannot distinguish between detectable compounds in a mixture
of gases, and therefore indicates an integrated response which is a function of
the response factors and concentrations of all ionizable species present.
The analyzer employs the principle of photo ionization for detection.
This process is termed photo ionization since the absorption of ultraviolet
light (a photon) by a molecule leads to ion izat ion as shown in the equation:
RH + h = RH++ e-
where RH = trace gas,
h = a photon with an energy >. I onization Potential of RH
The sensor consists of a sealed ultraviolet light source that emits
photons which are energetic enough to ionize many trace species (particularly
organics) but do not ionize the major components of air such as 02, N2,
CO, C02, or H20. A chamber adjacent to the ultraviolet source contains a
pair of electrodes. When a positive potential is applied to one electrode,
the field created drives any-ions formed by absorption of UV light to the
collector electrode where the current (proportional to concentration) is
measured. This signal is amplified and conditioned and then sent to the
output display.
To minimize adsorption of various sample gases, the ion chamber is
usually made of an inert fluorocarbon material. The sample line is kept as
short as possible, and a rapid flow of sample gas is maintained through the
ion chamber volume.
Uses
The portable photo ionization detector is useful as a general survey
instrument at waste sites and hazardous material spills. As such, it is
similar to an FID in application; however, its capabilities are somewhat
broader in that it can detect certain inorganic vapors. Conversely, the
PID is unable to respond to certain low molecular weight hydrocarbons (e.g.,
methane and ethane) that are readily detected by FID. In addition, certain
toxic gases and vapors (e.g., carbon tetrachloride, HCN) have high ionization
potentials and cannot be detected with a PID.
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Section 4.2.4
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Procedure for Use
The procedural steps delineated herein are intentionally general. The
operating manual for the unit being used should be consulted for specific
instructions.
1. Check battery charge level. If in doubt, charge battery as
described in manuaI.
2, Turn unit on. Verification of UV lamp operation can be made by
looking into sensor for purple glow of the lamp.
3, Perform zero and calibration procedure as described in operating
manual. Calibration for specific compounds can be performed so
that instrument response is proportional to the calibration gas
concentration.
4, If so equipped, set alarm at desired level.
5, Once calibrated, unit is ready for use.
6, Position intake assembly in close proximity to area in question as
the low sampling rate allows for only very localized readings.
7, A slow sweeping motion of intake assembly will help prevent the
by-passing of problem areas.
8, Be prepared to evacuate the area if preset alarm sounds. Operators
utilizing supplied air systems may not need to consider this action.
9, Static voltage sources such as AC power lines, radio transmissions,
or transformers may interfere with measurements. See operating
manual for discussion of necessary considerations.
10, Regular cleaning and maintenance of instrument and accessories will
assure representative readings.
11. As with any field instrument, accurate results depend on the
operator being completely familiar with the operator's manual for
the unit in use.
Sources
Systems Inc., "Instruction Manual for Model PI 101 Photoionization
Analyzer." 1975.
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4.2.5 METHOD IV-5: USE OF PORTABLE, FIELD-OPERABLE GAS CHROMATOGRAPHS
Discussion
The use of field portable gas chromatography (GC) for obtaining data on
concentrations of certain volatile organic compounds in ambient air in and
around waste sites has been demonstrated.3Whi Ie their ability to provide
unambiguous identification and quantitation of target compounds may be limited
by such factors as interferences, ambient conditions, and operator experience,
the data supplied in preliminary assessments using these instruments may be
used in determining air sampler placement and approximate compound
concentrations.
Gas chromatography is a technique in which components of a mixture are
separated in the gas phase using a solid phase sorbent. The mixture is placed
on the front end of GC column (generally a 1/8" stainless steel tube packed
with the appropriate sorbent) and flushed through the column with an inert
carrier gas. Compounds are eluted from the column according to such factors
as their affinity for the sorbent and volatility, and routed into a detector,
which may be designed to detect compounds having specific properties or may
respond to a more general class.
Identification of compounds is generally based on elution time from the
column. This retention time is dependent upon a number of factors; however if
these factors are held constant, retention times for individual compounds will
hold fairly steady. Standard mixtures of the compounds of interest are run to
determine retention times for the target compounds, and sample runs are
compared to identify specific eluting peaks.
While factors affecting retention time can be held constant in laboratory
settings, this may not be possible under field conditions, where lack of power
and variable environmental conditions may force compromises in the analysis.
A major factor affecting retention time, for instance, is temperature of the
GC column. Since the field portable GC's described here are designed to work
from battery power, sufficient energy may not be available to maintain the
column at constant temperature. Variations in ambient temperature will then
make retention times shift, making identifications ambiguous. Calibrations can
be run at several column (ambient) temperatures to provide a family of curves,
thus, reducing bias from temperature changes.
Another element contributing to ambiguous identification is complexity of
the sample. Compounds eluting with close or similar retention times may give
"false positive" identifications or false high quantitat ions. Quantitations
are based on comparison of response of sample components to response of
standards of known concentrations. Again, these values may be inaccurate due
to uncontrollable variables such as environmental conditions or sample
compI ex i ty.
Several detectors are available for as chromatography, ranging from the
very simple (such as thermal conductivity) to the more complex (such as mass
spectrometry). Due to power restrictions and other restraints, such as size
4-I7
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Section 4.2.5
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and reagent availability, field instruments have been limited to about three
or four detectors. The most common are:
Flame lonization Detectors (FID). The FID will respond to most
organic compounds as they form positively charged ions when
combusted in a hydrogen flame. The magnitude of the response is a
function of the detector sensitivity and the ionization properties
of the particular compound as well as its concentration. As a
result, this signal must be compared to that generated by calibration
with a known concentration of a standard. The output of the detector
is generally recorded on a strip chart recorder as intensity versus
retention time, producing a GC "peak". The area under the peak
(using an integrator) or the peak height at maximum intensity can
be used for quantitat ion. Maximum sensitivity is generally in the
mg/m3 (ppm) range.
Photo-lonization Detector (PID). The PID also ionizes sample
introduced into it and responds to positive ions produced by an
ultraviolet light source. Again, the magnitude of response is
dependent on concentration and ionization properties of the compound.
Response is measured as with the FID.
The PID offers two advantages over the FID. First, it is sensitive
to some compounds to the ug/m3(ppb) range, especially light aromatics
such as benzene, toluene, and xylene. Secondly, at least one model
(the HNu Model 301 Portable GC) can be equipped with lamps of differing
ionization potential, providing some degree of selectivity. Compounds
with ionization potentials above that of the energy of the lamp being
used exhibit vastly reduced response as compared to compounds with
lower ionization potential. For instance, toluene (ionization
potential 8.8 eV) will respond strongly when ionized by a 9.5 eV lamp,
while n-heptane (10.08 eV) will exhibit a greatly reduced response.
To assist in lamp selection, a listing of ionization potentials for
various compounds is typically included in the owner's manual.
The instruments listed below have been designed to be field portable or
are easily adaptable to field use, e.g. by addition of a battery pack or small
gas cyl inders.
Century Systems Model OVA-138 Organic Vapor Analyzer (OVA).4The
OVA-128 has two models: a "survey mode" to provide nonspecific
quantitat ion and/or detection of organic vapors (described more
fully in Method IV-3) and a GC mode, in which a gas chromatography
column is attached to the detector to possibly provide identification
of the vapor constituents. The OVA utilizes a flame ionization
detector (FID) which, in the survey mode, will yield sensitivities
to 0.1 ppm (methane). The instrument maintains its own power and
gas suppl ies.
Model 10A10 Photovac. This system uses a PID with a fixed ionization
potential. Sensitivities to 0.1 ppb for certain compounds have been
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reported.35 The system is almost completely self-contained, with
internal power and gas supplies, with only a strip chart recorder
external to the main body of the instrument.
HNu Model 301 Gas Chromatography. This unit is essentially a compact
laboratory instrument which is made field portable with the addition
of a "field pack", containing battery and gas supplies. Field-
usable detectors include an FID and a PID with a se let ion of lamps
ranging from 9.5-11.7 eV.
Sentex Sensing Technology Scentor Automated Gas Chromatography. This
is a relative new instrument utilizing an Argon lonization Electron
Capture or Flame lonization Detector. Sampling and analysis are
completely automated. Samples are collected on a sorbent cartridge,
then thermally desorbed into the GC column. The instrument maintains
a knowns standard gas internally for use in quantification.
Sensitivities for most organic compounds are reported at the low ppb
range and low part-per-tri I I ion range for polar compounds.6
Uses
In theory, any compound which can pass through a gas chromatographic
column as a discrete "peak" and is capable of being detected by the detector,
is amenable to this method. In practice, this may not always be the case.
A partial I ist of compounds measured in the field with portable GCs is given
in Table 4-1. Some of the factors which could be considered before using
a field portable GC in a field survey are as follows:
1. Column Selection. Selection of appropriate gas Chromatography column
packing and column length is necessary. A critical element in this
selection is the ability of the column to elute the compound(s)
of interest as a discrete "plug" at the temperature at which the
column will be operated.
Successful u e of two-column packings has been reported for general
purpose use:4 a 10 percent OV-101 on 60/80 mesh Chromasorb-W/AW-DCMS
treated and a 1 percent TCEP on 60/80 mesh Chromasorb W-HP. Spittler3
has reported use of a 12-inch carbowax column for rapid determination
of volatile loading and a 4-ft SE30 column for more efficient
separation and quantitat ion.
2, Compound Volatility. Generally, compounds exhibiting a vapor
pressure of less than 1 mm (Hg) at 20°C will be troublesome to
measure with a field-portable GC. Reasons for this include
adsorption of the components on unheated syringe walls, the
inability to elute the compound from the GC column at ambient
temperatures, and the GC's inability to measure particulate-bound
organic matter. Compounds in this class include PCBs, PAH, and
most pesticides.
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Section 4.2.5
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TABLE 4-1. COMPOUNDS SHOWN TO BE AMENABLE TO FIELD GC ANALYSIS4
Dichloromethane (methylene chloride)
Trichloromethane (chloroform)
Carbon tetrachloride
Dichloroethane (ethylene dichloride)
1,2-trans dichloroethylene
Trichloroethylene (TCE)
1,1,1-trichloroethane
TetrachIoroethyIene
Dimethyl ketone (acetone)
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Benzene
Methyl benzene (toluene)
Chlorobenzene
Ethyl benzene
Nitro benzene
1,2-dimethyl benzene (0-xylene)
1,3-dimethyl benzene (m-xylene)
1,4-dimethyl benzene (p-xylene)
Ethy I acetate
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The ability of a portable GC to provide unambiguous data may be
limited. It can, however, with proper use and data interpretation, be used
to detect and identify components of pockets of gaseous hydrocarbons in
depressions or confined spaces, vapors in drums or other containers, or in
ambient air.
Procedures for Use
The procedures presented in this section are intended to apply to any
protable GC; therefore, detailed operating instructions must be obtained from
the operating manual of the specific unit to be used. Some procedures, such
as the preparation of standards, can be used with any instrument, and these
are described here.
1. Standard Preparation
GC standards in air are prepared by using quantities of pure solvent
which are small enough to vaporize completely in a 40 ml VGA vial at ambient
pressure and temperature. To do this, 1 pi of the pure standard is injected
through the septum into the 40 ml vial. The resultant concentration is
caIcuIated by:
A x D
V + A
where: C = compound concentration (in ug/cc)
A = amount i nj ected (in u I)
D = density of the standard (in g/ml)
V = volume of the vial and the air in it (in liters)
For example, 1 ul of toluene is injected into a clean 40 ml.
VOA vial and allowed to vaporize. The resultant concentration is then
calculated as:
(1 ul) x (0.866 g/ml)
= 2.2 |jg/cc
(0.4 I)
This standard can then be used to prepare standards of lesser concentration by
further dilution with air on a volume/volume basis.
Several standards can be injected into one vial to make a
muIti-component standard to save calibration time. Care should be taken in
component selection to prevent the resultant chromatograms from being too
complex to determine individual compound responses. To extract a portion of
the vapor, penetrate the septum with a clean syringe and fill to the desired
volume. Remove the syringe and the standard is ready for injection into the
chromatography. Total volume removed should not exceed 1 ml. Volumes in
excess of 1 ml will detrimentally effect reproducibi I ity of standards.
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Section 4.2.5
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2, Sample Col lection
Samples can be collected and introduced into the GC by either of two
basic techniques: direct injection with a gas-tight syringe or, when so
equipped, through the gas sampling loop.
An air sample can be obtained with a gas-tight syringe at the
sampling site. The syringe is filled and emptied several times in the
contaminated atmosphere. The syringe is filled once again and the sample
is carried off site to an area where the GC is set up for field analysis.
The sample can then be injected into the GC column, a chromatogram produced,
and further qualitative/quantitative analysis performed. Sample volumes of
10 ul to 1 ml can be used.
Syringes may become contaminated if high concentrations of organics
are encountered. If a gas-tight syringe becomes contaminated, the easiest
method of cleaning is to bake it in the oven at 105°C overnight. It may be
possible to clean the syringe by removing the plunger, inserting the needle
into the injection port, and allowing carrier gas to flow through it for
several minutes.
Some instruments are equipped with a gas sampling loop to facilitate
sample collection and injection. This device is essentially a length of steel
tubing with a known volume that is fitted to the head of the chromatographic
column with a two-way valve. With the valve in the "load" position sample gas
can be drawn through the loop with a pump, then when the valve is switched to
the "inject" position, the loop is isolated from the pump system and the
carrier gas is diverted into the loop to sweep its contents onto the column.
The sample loop improves the consistency of the injections by assuring a
constant volume (provided temperature and pressure are constant) and a
cons i stent i nj ect i on speed.
3, Operation
a, Check battery charger level indicator; if in doubt, recharge
battery as described in the manual.
b, Turn instrument on and allow adequate warmup time.
c, Follow operating procedures for lighting FID flame (if used),
lighting PID lamp (if used), establishing carrier gas flow,
zeroing recorder response, etc.
d, Using the procedure described below, inject an appropriate
amount of the standard described in Section 1. Hold the
syringe in two hands, using one to guide the needle into the
septum and the other to provide force to pierce the septum and
to prevent the plunger from being forced out by the pressure
from the GC. Insert the needle through the septum as far into
the injection port as possible, swiftly and smoothly depress
the plunger, hesitate one second, and withdraw the needle.
4-22
-------
Sect i on 4.2.5
Rev i s i on 0
Page 7 of 14
e, Mark injection time and sample I.D. on output recorder strip
chart, and start timer for monitoring retention times. Record
pertinent parameters in analytical logbook for documentation of
analytical conditions.
f, Record retention times and peak heights (or integrated peak
areas if an integrator is available) of each e luting peak.
n Chromatograms of blank injections should be made at frequent
intervals, especially after running a sample with a high
contaminant loading, to guard against syringe contamination.
h, At least one standard run should be made on each day of
analysis, or when conditions change sufficiently to-warrant
re-caI ibrat ion.
4, Compound Identification
Injection of standard mixtures of compounds will allow determination
of retention time for each of the compounds. The elution order of the compounds
in these mixtures will remain constant for a given GC column and should be
determined prior to field use. Tables 4-2 through 4-4 give elution orders and
approximate retention times for several compounds on several columns.
After both standards and samples have been run, comparison of the samples
to standards should be made. If retention time matches are noted, another
column is installed in the GC and standards and samples re-run, with subsequent
comparisons made. A retention-time match on two different columns provide a
fairly reliable identification, however, given the purpose of this screening,
the data should be labeled "tentative" or "preliminary".
To save analytical time, the following strategy has been used. Since
shorter GC columns result in shorter retention times at the cost of lower
resolution between peaks, a short column is used to do the first set of
analyses, and longer columns are used to verify compound identity and
quantitat ion.
5, Quantitat ion
Following tentative identification of compounds in the sample, a
determination of quant i tat ion can be made. This can be based either on peak
height or on the integrated area under the peak if an integrator is used.
First, using the response to the standard, calculate a response
factor as:
R
V x C
4-23
-------
TABLE 4-2. SELECTED RETENTION TIMES 8-INCH 3 PERCENT DIISODECYL PHTHALATE ON CHROMASORB W
Compound
OeC
Time, Seconds
40°C
Compound
Time, Seconds
Freon 113
Pentane
Ethhanethiol
Yinylidene Chloride
Hexane
Methylene Chloride
Methyl Acetate
Acrylonitrile
Vinyl Acetate
Ethrane
Methyl Alcohol
Halothane
Acetonitrile
Acetone
Trichloroethane 1,1,1
Heptane
Methyl Aerylate
Ethyl Acetate
Benzene
Chloroform
.6
.1
.6
.5
15.3
18.0
18.0
19.8
21.
26.
30.
31.
32.4
36.0
36.9
36.9
36.9
36.9
40.5
45.9
48,
49.
49,
51.3
Pentane
Vinylidene Chloride
Hexane
Freon 113
Ethrane
Ethanethiol
Methylene Chloride
Vinyl Acetate
Trichloroethane 1,1,1
Methyl Acetate
Halothane
Chloroform
Acetonitrile
Heptane
Ethyl Acetate
Acrylonitrile
Methyl Acrylate
Ethylene Dichloride
Acetone
Methyl Ethyl Ketone
11.7
12.6
12.6
12.6
12.6
12.6
14.4
15
15
16
17
17
17
18
18
18
19.8
19.8
19.8
21.6
(continued)
"d TO CO
CD 05 05
CO < O
05 rl-
(/)
oo-o
ho
-------
TABLE 4-2 (continued)
0°C
Compound
Time, Seconds
Compound
40°C
Time, Seconds
Tetrahydrofuran 65.7
Ethylene Dichloride 66.6
Trichloroethylene 76.5
Methyl Ethyl Ketone 76.5
Ethyl Acrylate 95.4
Methyl Methacrylate 100.8
Toluene 133.2
Tetrachloroethylene 171.0
Propanol, N 182.7
Methyl Isobutyl Ketone 278.1
Trichloroethane 1,1,2 313.2
Ethylene Dibromide 320.4
Ethyl Benzene 369.9
Styrene 677.7
Pyridine 1000.0
Pentanol 1000.0
Butyl Acrylate 1000.0
Methyl Alcohol
Benzene
Tetrahydrofuran
Trichloroethylene
Ethyl Acrylate
Methyl Methacrylate
Toluene
Propanol, N
Methyl Isobutyl Ketone
Tetrachloroethylene
Trichloroethane 1,1,2
Ethylene Dibromide
Ethyl Benzene
Butyl Acrylate
Styrene
Pentanol
Pyridine
21.6
21.6
22.5
23.4
26.1
27.0
37.fi
38.7
39.6
43.2
54.0
.4
.5
59.
67.
108.0
117.0
163.8
1000.0
(continued)
"d 73 CO
03 05 05
CO < O
05 (-1-
(/)
CD O
ho
-------
TABLE 4-3. SELECTED RETENTION TIMES 8-INCH 10 PERCENT OV-101 ON CHROMASORB W GC COLUMN
Compound
0°C
Time, Seconds
40°C
Compound
Time, Seconds
ho
CD
Methyl Alcohol
Ethanethiol
Vlnylidene Chloride
Pentane
Ethrane
Acetone
Methylene Chloride
Methyl Acetate
Freon 113
Acetonitrile
Acrylonitrile
Halothane
Vinyl Acetate
Methyl Ethyl Ketone
Propanol, N
Hexane
Chloroform
Methyl Aerylate
Ethyl Acetate
Tetrahydrofuran
21.3
23.9
25.
25.
25,
27.
30.1
30.1
30.1
30.1
31.0
35.4
43.
48.
49.
49.6
55.8
56.7
59.4
64.8
.2
.7
.5
Pentane
Ethrane
Ethanethiol
Methyl Acetate
Acetone
Methylene Chloride
Methyl Alcohol
Halothane
Freon 113
Vinylidene Chloride
Acetonitrile
Vinyl Acetate
Acrylonitrile
Methyl Ethyl Ketone
Hexane
Ethyl Acetate
Chloroform
Propanol, N
Ethylene Dichloride
Methyl Aerylate
11.5
12.4
12.4
13
13
14
14
14
14
14.4
15.9
16.9
16.8
18.6
18.6
18.6
18.6
.3
.3
.2
.2
.2
.2
19.8
21.3
21.3
(continued)
"D 731 CO
CD 05 05
CO < O
05 (-1-
(/>
O O Z!
O J^
-h o -
hO
en
-------
TABLE 4-3 (continued)
0°C
Compound
Time, Seconds
40°C
Compound
Time, Seconds
hO
Ethylene Dichloride
Trichloroethane 1,1,1
Benzene
Tri chloroethylene
Ethyl Acetate
Heptane
Methyl Methacrylate
Methyl Isobutyl Ketone
Trichloroethane 1,1,2
Toluene
Pyridine
Ethylene Dibromide
Pentanol
Tetrachloroethylene
Ethyl Benzene
Styrene
Butyl Aery late
68.2
70.2
78.8
121.5
124.9
134.
141.
182.
.6
,7
.5
225.0
.2
,7
.4
241,
254.
291.
360.0
367.2
571.4
916.2
1000.0
Tetrahydrofuran 22.5
Trichloroethane 1,1,1 23.0
Benzene 24.8
Ethyl Acrylate 25.7
Trichloroethylene 27.5
Heptane 30.1
Methyl Methacrylate 31.0
Methyl Isobutyl Ketone 37.2
Trichloroethane 1,1,2 41.6
Toluene 45.0
Methyl Acrylate 56.7
Ethylene Dibromide 56.7
Tetrachloroethylene 65.7
Pentanol 77.4
Pyridine 85.5
Ethyl Benzene 94.8
Styrene 118.8
~O TO CO
CD 05 05
CQ < o
05 (-1-
(/)
* O
-> O Z!
O -1^
-h o -
hO
-t* en
-------
TABLE 4-4. SELECTED RETENTION TIMES 8-INCH 1 PERCENT TCEP ON CHROMASORB W-HP
0°C
Compound
Time, Seconds
Compound
40°C
Time, Seconds
ho
oo
Pentane
Freon 113
Hexane
Vinylidene Chloride
Heptane
Ethanethiol
Trichl oroethane 1,1
Halothane
Methyl ene Chloride
Methyl Acetate
Ethrane
Trichl oroethyl ene
Tetrahydrofuran
Acetone
Vinyl Acetate
Benzene
Chloroform
Ethyl Acetate
Methyl Acrylate
Methyl Alcohol
13.5
16.2
19.8
21.6
26.1
26.1
,1 51.3
57.6
63.0
79.2
81.9
84.6
97.2
98.1
99.0
102.6
107.1
126.0
138.6
143.1
Pentane
Hexane
Freon 113
Vinylidene Chloride
Ethanethiol
Heptane
Halothane
Ethrane
Trichloroethane 1,1,1
Methyl ene Chloride
Methyl Acetate
Trichl oroethyl ene
Acetone
Ethyl Acetate
Vinyl Acetate
Tetrahydrofuran
Chloroform
Benzene
Tetrachl oroethyl ene
Methyl Ethyl Ketone
11.7
12.6
12.6
14.1
14.4
16.2
18.9
18.9
21.6
23.4
23.4
27.9
27.9
28.8
29.7
29.7
30.6
32.4
36.0
39.6
(continued)
"d TO CO
CD 05 05
CO < O
05 (-1-
_1 O
hO O Z!
Z3
O J^
-h o -
hO
-------
TABLE 4-4 (continued)
0°C
Compound
Time, Seconds
Compound
40°C
Time, Seconds
Tetrachloroethylene
Methyl Ethyl Ketone
Acrylonitrile
Ethylene Dichloride
Toluene
Methyl Methacrylate
Ethyl Acrylate
t" Acetonitrile
08 Propanol, N
Methyl Isobutyl Ketone
Ethyl Benzene
Trichloroethane 1,1,2
Styrene
Pyridine
Pentanol
Ethylene Dibromide
Butyl Acrylate
.1
.1
.5
152.
179,
202.
225.0
232.2
247,
247,
.5
.5
324.0
340.2
450.0
464.4
1000.0
1000.0
1000.0
1000.0
1000.0
1000.0
Methyl Acrylate
Methyl Alcohol
Toluene
Acrylonitrile
Ethylene Dichloride
Ethyl Acrylate
Methyl Methacrylate
Propanol, N
Methyl Isobutyl Ketone
Acetonitrile
Ethyl Benzene
Ethylene Dibromide
Butyl Acrylate
Trichloroethane 1,1,2
Styrene
Pentanol
Pyridine
41.4
45.0
48.
49.
50.
50.
54.
61,
69.
69.
87.
162.
165.6
167.4
208.8
216.0
1000.0
.6
,5
.4
.4
.9
,2
,3
,3
,3
.9
~O TO (S)
0> 05 05
to < o
05 (-1-
(/)
_i O
GO O Zi
O .£
-h o -
-------
Sect i on 4.2.5
Rev i s i on 0
Page 14 of 14
where: RF = response factor
C = concentration of the standard (ug/ml)
V = volume of standard injected (ml)
R = response to the standard (in integrated counts or measured
I inear dimensions).
Sample concentrations can then be estimated by:
R1
where: C1 = sample concentration (ug/ml)
R1 = response of sample peak (in the same units as used for the
standard)
V1 = volume of sample injected (ml)
RF = calculated response factor.
4-30
-------
Sect i on 4.2.6
Revision 0
Page 1 of 2
4.2.6 METHOD IV-6: STAIN DETECTOR TUBE METHOD FOR SAMPLING GASEOUS COMPOUNDS
Discussion
A relatively simple method for determining concentrations of specific
gaseous pollutants is through the use of stain detector tubes. They are
usually calibrated in ppm for easy interpretation and are either direct reading
or referenced to a supplied concentration scale or color change chart. The
limiting factors in the application of this methodology are the small number
of compounds for which detector tubes are available, interfering agents and
cross-sensitivities, short sampling time, and the extremely small sample volume
used. Most detector tubes are species specific; however, some detect groups of
compounds, e.g., "total hydrocarbons."
The detector tubes are specific for individual compounds and require
specific sampling techniques. This information is supplied with the tubes and
details the required sample volume, proper tube preparation and insertion into
the pump, and a discussion of the appl icabi I ity and I imitations of the tube.
In general the tubes are opened by snapping off the tips on either end and
inserting them into the pump so that the arrow on the tube indicates flow
toward the pump. The required sample volume is then pulled through the tube.
An indicator chemical in the tube will demonstrate a color change, the length
of which is proportional to the concentration of the compound in question.
The detector tube and pump are the two major components of the system.
Pumps used for drawing air through the tubes come in two basic forms: bellows
pump and piston-type (syringe). These pumps are manufactured under strict
specifications so as to draw only a specified volume of gas and are designed
to be used with tubes of the same manufacturer.
Uses
Stain detector tubes are useful for screening sources to verify the
Presence of suspected compounds and to provide some degree of quantification.
They are generally inadequate for ambient air sampling applications due to the
low sample volumes collected. They are more useful for detection of compounds
at higher levels such as in drums, confined work areas, pockets or depressions,
etc.
Procedure for Use
1. Perform necessary pump leak check procedures. This is usually
accomplished by plugging pump inlet, drawing a vacuum on the pump,
holding it for at least 1 minute and determining visually if leak
allows bellows to inflate or piston fails to return completely
into pump. The pump can be plugged using a sealed detector tube.
4-3I
-------
Section 4.2.6
Rev i s i on 0
Page 2 of 2
2, Break open both ends of detector tube, insert correct end into
pump, and sample according to instructions. Most tubes have some
kind of indicator (i.e., arrow, prefi Iter) that helps determine
which end of tube is the inlet. The direction of the
concentration scale is also a guide.
3. Visually inspect tube for color changes and record corresponding
gas concentration.
4, Additional Notes
Prior to use, check tube expiration date, because most have
a defined shelf I ife.
Some tube manufacturers advise that tubes showing negative
results can be reused before they are rendered useless. The
error potential and risk associated with reusing a previously
opened tube is not advisable when working with hazardous
materia Is.
Some types of detector tubes have reagent ampules which must be
broken to activate the indicator. Also, some procedures call
for use of multiple tubes, in series for multiple parameter
detection, or specific interference removal.
The standard range of measurement or the detector sensitivity
can sometimes be extended by changing the number of pump volumes
pulled through the tube. The upper range limit can be extended
by decreasing the number of pump volumes, and the lower range
limit can be extended by increasing the number of pump volumes.
Tubes and pumps of different manufacturers should not be used
interchangeably. For example, Drager tubes should be used only
with Drager pumps.
Sources
Dragerwerk Ag Lubeck. "Detector Tube Handbook, Air Investigations and
Technical Gas Analysis with Drager Tubes." 4th Edition, August 1979.
Matheson Safety Products. Operating Instructions for Matheson-Kitagawa
Detector Tubes, Matheson Gas Products Model 8014 - Toxic Gas Detector.
4-32
-------
Section 4.2.7
Rev i s i on 0
Page 1 of 15
4.2.7 METHOD IV-7: SAMPLING FOR VOLATILE ORGAN ICS IN AMBIENT
AIR USING SOLID SORBENTS
Discussion
Solid sorbent cartridges can be used quite successfully to collect
samples of volatile organics in ambient air and workplace environments. The
sample apparatus consists of a sampling cartridge packed with a solid sorbent
of desirable characteristics (e.g., Tenax-GC, activated charcoal, XAD-2) and a
pump system capable of maintaining a constant flow rate across the collection
media for a specified period of time.
In principle, organic vapors present in the air are adsorbed on the
collection media and subsequently desorbed, thermally or chemically, in the
laboratory. An aliquot of the desorbed sample is then subjected to
chromatographic analysis (either capillary or packed column) followed by flame
ionization or mass spectrometric detection.
Although several sorbents or sorbent combinations have been utilized for
collection and concentration of volatile organic species, at present the porous
polymer, Tenax-GC, is the most widely studied for a wide variety of compounds
at concentrations typically found in ambient air. Tenax-GC is hydrophobic,
thermally stable up to 360°C, and permits thermal resorption of organic species
with volatility greater than n-eicosane at temperatures of 280°C.'Glass or
glass-lined stain less-steel sampling cartrides of various sizes and
configurations are available and can be purchased prepacked or packed to
specifications in the laboratory. In any case, the sorbent and/or prepacked
tubes must be thoroughly precleaned, conditioned, and checked for freedom from
interferences prior to use.
Other sorbents or combination of sorbents may be applied with equal
success depending upon the nature of the ambient environment and the specific
species of voI at lies under investigation. Monsanto Research Corporation
reports success with a combination sorbent system based on Tenax-GC, Porapak R,
and Ambersorb XE-340 which has been used to collect a broad range of organic
compounds.8NIOSH procedures may also be used and the "NIOSH Manual of
Analytical Methods"9 should be consulted where applicable. Finally, if the
detection of specific organics is desired, the characteristics of the compound
and sorbent of interest should be researched91011 and all sampling parameters
adjusted to meet these criteria.
The recommended procedure131415 involves prec lean ing a batch of Tenax
by Soxhlet extraction in methanol first, and then pentane for 24 hours each.
The sorbent is then oven dried, packed in tubes and conditioned under carrier
gas flow at 270°C (resorption conditions for 4 hours). The conditioning can be
performed a final time (1 hour run) just prior to use. Cartridges are then
stored in Teflon-capped culture tubes packed in aluminum foil, and then in 1
gallon "paint cans," for shipment to and from the field. Culture tubes should
be wrapped in foil to limit exposure of sampling cartridges to UV light.
Analysis should be instituted as quickly as possible in order to prevent sample
4-33
-------
Section 4.2.7
Revision 0
Page 2 of 15
degradation. Schlitt, et a I.,7 recommend a maximum storage time of 48 hours;
however, this is often impractical, and a maximum storage period of 30 days has
been used successfully in a previous study.1516 In any event, sorbent cartridges
should be transported in solvent free coolers packed with "blue ice" and stored
at 4°C while awaiting analysis.
The outlined procedure utilizes a borosilicate glass tube, outside
diameter 16 mm (5/8") by 10 cm in length. The tube is packed with 1.2 grams
of Tenax-GC sorbent with a plug of glass wool at each end (double plug at
inlet). The personal monitoring pumps can be any low-flow model capable of
maintaining consistent flows at the rates prescribed. Personnel monitoring
pumps are available from a number of vendors and range in sophistication (and,
accordingly, price) from very simple models to programmable ones capable of
compensating for increasing pressure differential in addition to other
features. Care should be taken to select a pump capable of operating in the
desired flow rate range and which has features most likely to be used by the
investigator.
Due to the wide range of volatility and breakthrough volumes of compounds
amenable to this method, it is recommended that samples be collected at widely
different flow rates and therefore different volumes. This approach will
guard against analytical system overload and breakthrough of the more volatile
organics while at the same time maintaining maximum sensitivity for all
compounds. To achieve this, four (4) samplers are placed at each desired
location and run for a specified time period (usually 4-8 hours). As a
general guideline, one sampler should be operated within each of the following
ranges.
Flow Rate Range TotaI VoIume
10- 20 cc/min 5-10 I iters
20- 40 cc/min 10-20 I iters
40- 80 cc/min 20-40 I iters
80-160 cc/min 40-80 I iters
This approach is based upon Standard Operating Procedures (SOPS) in
use at EPA's Environmental Monitoring Systems Laboratory (EMSL) at Research
Triangle Park (RTP), North Carolina. It is highly recommended for those
cases where I ittle is known about the compounds and concentrations present
at a given site. The procedure can be costly, however, due to the potential
number of samples that could be generated for subsequent analysis. Time
and cost constraints may therefore dictate a compromise (collection of fewer
samples/location) which may unfortunately jeopardize the quality of the
resultant data. It is therefore recommended that as much background
information concerning suspected compounds and approximate concentrations be
collected as possible before deciding on a compromised approach. It is also
recommended that at a minimum, the delineated procedure be adhered to for
undefined situations.
4-34
-------
Sect i on 4.2.7
Revision 0
Page 3 of 15
Uses
The method outlined below has been successfully used for quantitative
analysis of the compounds listed in Table 4-5 in ambient air and is based on
procedures used successfully for qualitative and quantitative analysis during
several programs. A brief review of the literature71718192021 reveals
that a number of additional compounds (Table 4-6) have been analyzed either
qualitatively or quantitatively using modifications of the procedure described
herein. Other additional compounds may be amenable to the method, and to aid
in determining both applicability and appropriate sampling volumes, a I ist of
retention volumes for the described sorbent tube has been included as Table
4-7. It should be noted, however, that since many of the compounds included in
these lists have not been analyzed using this specific method, testing or
further review should be performed to perfect and prove the method for these
compounds prior to actual sampling and analysis.
Procedures for Use
1. Calibration of Sampling Pumps Equipped with Rotameter, Needle Valve
Combination--
a, Select a set of sampling pumps and assemble necessary equipment
(see Figure 4-1). Calibrate each pump as follows:
b, Measure ambient air temperature, barometric pressure and
relative humidity. Determine water vapor pressure from tables.
c, If battery test is available, check battery.
d, Place "calibrator" sorbent cartridge in line and start pump.
Allow pump to stabilize. Do not use this "calibrator" cartridge
for actual sampling, however, it can be reused for additional
cal ibrat ion runs.
e, Determine actual flow rate, f, with bubble tube flowmeter.
Distance traveled (ml)
f =
Travel time (min)
Adjust flow rate of the sampler to the desired rate by adjusting
the needle valve. Verify that the flow rate has been achieved by
checking against bubble tube three times. Calculate a mean
value by summing the values of the three individual readings and
dividing by three. The deviation of the individual flow rates
from the mean flow rate should not exceed ±5 percent.
4-35
-------
TABLE 4-5. COMPOUNDS SUCCESSFULLY MONITORED
TENAX SAMPLING PROTOCOLS22
Sect i on 4.2.7
Revision 0
Page 4 of 15
USING
2-Chloropropane
1,1-Dichloroethene
Bromoethane
I-Chloropropane
BromochIoromethane
ChIoreform
Tetrahydrofuran
1,2-D ichloroethane
1, 1,1-Trichloroethane
Benzene
Carbon tetrachloride
Dibromethane
1,2-Dichloropropane
Trichloroethene
1, 1,2-Trichloroethane
2,3-D ichlorobutane
Bromotr i chIoromethane
To Iuene
1,3-D i chIoropropane
1,2-Di bromethane
TetrachIoroethene
Chlorobenzene
1,2-Di bromopropane
N itrobenzene
Acetophenone
Benzon itrite
Iso-propylbenzene
p-1sopropyI to Iuene
1-Bromo-3-chIoropropane
Ethyl benzene
Bromoform
EthenyI benzene
o-Xylene
1,1,2,2-TetrachIoroethane
Bromobenzene
Benzaldehyde
PentachIoroethane
4-Chlorostyrene
3-ChIoro-1-propene
1,4-Dichlorobutone
1,2,3-Tr i chIoropropane
1,1-Dichloroethane
2-Chlorobutane
2-Chloroethyl vinyl ether
1,1,1,2-TetrachIoroethane
p-Dioxane
Epichlorohydron
1,3-Dichlorobutane
p-D i chIorobenzene
cis-1,4-Dichloro-2-butene
n-Butyl benzene
3,4-D i chIoro-1-butene
1,3,5-Tr i methyI benzene
4-36
-------
Section 4.2.7
Rev i s i on 0
Page 5 of 15
TABLE 4-6. LITERATURE SUMMARY - VOLATILE ORGAN ICS AMENABLE
TO COLLECTION BY TENAX SORBENT CARTIDGES
Component Reference(s)
N-Nitroso dimethyl amine 17
6-Propiolactone 17
Ethyl methansuIfonate 17
Nitromethane 17
GlycidaIdehyde 17
Butadiene diepoxide 17
Styrene Epoxide 17
Ani I ine 17
Bis (chloromethyl) ether 17
Bis (2-chloromethyl) ether 17
Diethyl Sulfate 18
Acrolein 18
Propylene Oxide 18
Cyclohexene Oxide 18
Styrene Oxide 18
Acetophenone 18,
Methanol 20
Ethanol 20
Propanol 20
Ethy I Acetate 20
Acetone 20,
1,2,4-Trichlorobenzene 21
1,2,3,5-TetrachIorobenzene 21
Hexachlorobenzene 21
p-Chlorophenol 21
2,4,6-Trichlorophenol 21
Diphenyl Oxide 21
o-Phenyl phenol 21
Pentachlorophenol 21
n-Pentane 7
2-Methyl pentane 7
3-Methyl pentane 7
n-Hexane 7
Heptane 7
n-Octane 7
n-Nonane 7
PropyI benzene 7
Trimethyl benzene 7
o-EthyI toluene 7
4-37
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Sect i on 4.2.7
Revision 0
Page 6 of 15
TABLE 4-7. APPROXIMATE RETENTION VOLUMES AT 38°C (100"F)
(I itens/gram of Tenax)
Am i nes
Ethers
Esters
Ketones
Aldehydes
Alcohols
Aromat i cs
Hydrocarbons
Halogenated
Hydrocarbons
d i methy 1 am i ne
isobutylamine
t- butyl am ine
d i - (n-buty 1 )amine
pyr id ine
di ethyl ether
propylene oxide
ethy 1 acetate
methyl aery late
methyl methacrylate
acetone
methy 1 ethy 1 ketone
methy 1 v i ny 1 ketone
acetophenone
aceta 1 dehyde
benzaldehyde
methanol
n-propanol
a 1 ly 1 a Icohol
benzene
toluene
ethyl benzene
cumene
n-hexane
n-heptane
2 , 2-d i methy 1 butane
2,4-dimethylpentane
4 -methyl- l-pentane
cyclohexane
methyl chloride
methyl bromide
vinyl chloride
0.8
9
0.8
1200
56
4
3
20
20
70
3
10
10
860
0.6
920
0.3
4
5
19
97
200
440
5
20
0,1
20
3
8
2
0,8
0,5
(continued)
4-38
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Section 4.2.7
Rev i s i on 0
Page 7 of 15
TABLE 4-7 (continued)
Halogenated
Ethers
Nitrosamines
Oxygenated
Hydrocarbons
methylene chloride
chloroform
carbon tetrachloride
1,2-d ichloroethane
1,1,1-trichloroethane
tetrachIoroethene
trichIoroethene
1,chIoro-2-methyIpropene
3-chIoro-2-methyIpropene
1,2-dichloropropane
1,3-dichloromopane
epichlorohydrin (1-chloro-2,3-epoxy propane)
3-chloro-1-butane
allyl chloride
4-chloro-1-butene
1-chloro-2-butene
chlorobenzene
o-d i chIorobenzene
m-d ichIorobenzene
benzyl chloride
bromoform
ethylene dibromide
bromobenzene
2-chloroethyI ethyl ether
B i s-(chIoromethyI)ether
N-n i trosod i methyI am i ne
N-n i trosod i ethyI am i ne
acrolein
glye IdaIdehyde
propylene oxide
butadiene diepoxide
eye Iohexene ox i de
styrene oxide
10
6
80
20
6
7
30
90
30
5
4
10
20
150
300
400
500
100
60
300
70
120
90
420
3
40
4
210
330
930
(continued)
4-39
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Sect i on 4.2.7
Rev i s i on 0
Page 8 of 15
TABLE 4-7 (continued)
phenol 330
acetophenone 600
B-propiolactone 100
Nitrogenous nitromethane 9
Hydrocarbons aniline 680
Sulfur diethyl sulfate 1
Compounds ethyl methane sulfate 830
4-40
-------
TUBING
GRADUATED
BURETTE ^
^-*
.
SOAP
SOLUTION ^
1
<
_
1C
_ f
__l
-|
J
1
1
v
* '
,
-
1
^
^
/-CALIBRATOR
if SORBENT
CARTRIDGE
r NEEDLE VALVE
/ ADJUSTMENT CONTROL
A
SAMPLING
PUMP
O
^-ROTAMETER
f
"O TO CO
03 05 CD
Figure 4-1. Calibration schematic for rotameter and needle valve combination.
O -
-------
Sect i on 4.2.7
Rev i s i on 0
Page 10 of 15
g. Calculate flow rate at standard conditions as follows:
Tc Pstd
Nomenclature--
F = flow rate at standard conditions, liters/min (ftVmin)
f = actual flow rate at calibration conditions, liters/min
(ftVmin)
Tc = temperature of air during calibration, °K (°R)
Pc = pressure of air during calibration, mm Hg (in. Hg)
Tstd = standard absolute temperature, 298°K (537°R)
Pstd = standard absolute pressure, 760 mm Hg (29.92 in. Hg)
PH2o = vapor pressure of water at Tc, mm Hg ( in. Hg)
h, Mark level achieved during flow rate setting on rotameter and
record on sampling data sheets for reference. To ensure
acceptable flow rate precision, this reference setting on the
rotameter should be maintained during sampling. The rotameter
can either be integral with the pump (as in the MSA Monitaire
Model S) or separate.
i, Note that, in this case, the rotameter is used only as a visual
reference. To ensure correctness of the reference point,
calibration conditions should not deviate from sampling
conditions by more than the following:
Temperature ± 15°C
Barometric pressure ± 10 mm Hg.
Calibration of Constant Flow Pump Systems--
a, Select a set of sample pumps and assemble necessary equipment.
Figure 4-2 depicts a calibration set-up developed by E.I. DuPont
de Nemours and Company for use with their constant flow sampling
pumps. This configuration or equivalent is acceptable.
b, Calibrate each pump according to the following basic steps. In
addition, consult the manufacturer's instructions for specific
details unique to the model in use.
4-42
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Sect i on 4.2.7
Rev i s i on 0
Page 11 of 15
FLOW RATE METER
( cc/min or I/mm )
FLOW RATE
METER
ADJUSTMENT
VALVE
t
t
^\y
\
PRESSURE DROP METER
i0-50 in M20)
PRESSURE DROP
VALVE
BUBBLE
TUBE
AIR IN
CONSTANT
FLOW SAMPLER
CALIBRATOR
CONSTANT FLOW
SAMPLING PUMP
DISH WITH
BUBBLE
SOLUTION
Figure 4-2. Calibration configuration for constant flow samplers.
4-43
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Sect i on 4.2.7
Revision 0
Page 12 of 15
c, Measure ambient air temperature, relative humidity, and
barometric pressure. Determine water vapor pressure from
tab Ies.
d, If battery test is available, check battery.
e, Connect pump inlet to bubble tube flowmeter* and start pump.
Allow pump to stablize before taking readings.
f, Adjust to desired flow rate. With the calibration configuration
depicted in Figure 4-2, the flow rate can be adjusted to the
target range with the magnehelic flow rate meter.
9" If a flow rate meter is not available, determine the initial
flow rate using the bubble tube flow meter and record the time
required for the bubble to travel between the appropriate volume
markings on the tube.
h, CaIcuI ate the actuaI fIow rate as f o I Iows:
Distance traveled (ml)
f =
Travel time (min)
i, Once the flow rate of each sampler has been adjusted to the
appropriate setting, verify three times with the bubble tube and
record the results. Calculate the mean flow rate by summing the
values of the three individual readings and dividing by three.
The deviation of the individual flow rates from the mean flow
rate should not exceed ± 5 percent.
j, Calculate flow rate and total sample volume at standard
conditions as follows:
pstd
Nomenclature--
F = flow rate at standard conditions, liters/min (ftVmin)
*Constant- flow type pumps such as the DuPond P-4000 have the ability to
maintain the flow rate with ± 5 percent at pressure drops as high as
25 inches of water. For this reason, it is unnecessary to place a
"calibrator" sorbent cartridge in line as long as the expected pressure
drop does not exceed that specified by the manufacturer.
4-44
-------
Sect i on 4.2.7
Rev i s i on 0
Page 13 of 15
f = actual flow rate at calibration conditions, liters/min
(ftVmin)
Tc = temperature of air during calibration, °K (°R)
Pc = pressure of air during calibration, mm Hg (in. Hg)
Tstd = standard absolute temperature, 298°K (537°R)
Pstd = standard absolute pressure, 760 mm Hg (29.92 in. Hg)
PHZO = vapor pressure of water at Tc, mm Hg (in. Hg)
k, When using the calibration configuration depicted in Figure 4-2,
the flow maintenance feature of the pump can be checked by
inducing a pressure drop across the system using the pressure
drop valve and determining the subsequent flow rate with the
bubble tube. The maximum difference between the flow rate
determined in step i and the flow rate measured at the maximum
expected pressure drop should not exceed ± 5 percent.
Sampling Procedure--
a, Assemble sampling train (Figure 4-3). The general procedure
requires four trains operated within the flow rate ranges listed
in the preceding discussion be set up at each location.
Duplicate sampers operating at the same flow rate as one or more
of the listed ranges can be set up to collect duplicate samples
for backup or quality assurance purposes. Set trains up at
desired location and hang samplers on a tripod, music stand, or
similar device. To insure stability in wind gusts, weighting of
these devices or some method of anchoring is advisable.
Nonsparking wooden stakes or fence post can be used but are more
work, more difficult to move (which is often necessary), and may
incur more risk where buried hazards exist.
b, Record all initial information (time, counter reading, cartridge
number, pump number, sampler, blank number, barometric pressure,
ambient temperature, relative humidity, etc.).
c, Start pump and observe system to determine if appropriate flow
rate is being maintained. For systems utilizing rotameters,
the calibrated rotameter setting should be maintained during the
entire run and should be monitored regularly. Any adjustments
to the rotameter are made by opening or closing the needle valve
and are noted in the field log. Most constant flow sampling
pumps have low flow indicators and/or an automatic shut-off
feature at low flow conditions. These should be initially
observed and periodically monitored during the course of
sampling. 4_45
-------
TUBING
PARTICULATE FILTER
(OPTIONAL)
MOISTURE TRAP
(OPTIONAL)
PYREX TUBE
PREFILTER OR PACKING
Sect i on 4.2.7
Rev i s i on 0
Page 14 of 15
PUMP
TENAX SORBENT PLUG
TRIPOD,
ADJUSTABLE
HEIGHT
Figure 4-3. Tenax sampler.
4-46
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Sect i on 4.2.7
Revision 0
Page 15 of 15
Allow pump to run for desired sampling time.
e, At the end of the sampling period, observe rotameter level or
low flow indicator to determine if flow rate has been
maintained. Shut down sampling pump and record all pertinent
information (counter reading, time, barometric pressure,
relative humidity, ambient temperature, problems, comments,
etc.). The final flow rate should not deviate from the initial
flow rate by more than ± 5 percent.
f, Remove sorbent cartridge (use clean lint-free gloves) and place
in culture tube. Place cartridge in culture tube with the inlet
facing up and mark accordingly on the outside of the culture
tube. Do not put any marking on Tenax cartridges.
g. Place plugs of glass wool below and above the cartridge and
tightly cap and label the culture tube. Before proceeding with
the packing, the tube should be shaken to insure that the
cartridge does not rattle inside the culture tube.
h, Place sample identification tag on culture tube and fill out
chain-of-custody form.
i, Calculate total sample volume at standard conditions
Vstd = F x t
where
F = flow rate at standard conditions, liters/min (ftVmin)
t = total sample time (min)
Vstd = sample gas volume at dry standard conditions, dsl (dscf)
Sources
GCA Corporation. "Quality Assurance Plan, Love Canal Study, Appendix A,
Sampling Procedures." EPA Contract 68-02-3168.
GCA Corporation. "Guidelines for Air Monitoring at Hazardous Waste Sites
for Volatile and Semi volatile Organic Compounds Using Tenax and
Polyurethane Foam Sorbents." EPA Contract 68-02-3168. April 1983.
4-47
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Section 4.2.8
Revision 0
Page 1 of 7
4.2.8 METHOD IV-8: COLLECTING SEMI VOLATILE ORGANIC COMPOUNDS IN AMBIENT
AIR USING POLYURETHANE FOAM (LOW VOLUME SAMPLERS)
Description
Polyurethane foam (PUF) has been shown to be an excellent collection
media for trapping and concentrating a variety of semi-volati le organic
compounds (defined here as exhibiting a vapor pressure less than or equal to 1
mm (Hg) at 20°C). Foams plugs are cut from the type of PUF used for furniture
upholstery, pillows, and mattresses and is Soxhlet extracted with high grade
hexane (pesticide quality or equivalent) prior to being fitted into specialized
sampling cartridges. To sample airborne organics, a known volume of air is
drawn through the collection media.
Cylindrical polyurethane foam plugs (polyether type, 0.021 gm/cm3) are
cut from 3-inch stock using a 25 mm circular template, then cleaned in a
soxhlet extractor to remove potential interferences. After drying to remove
excess solvent and analyzing of one plug from each batch to verify freedom
from contamination, the plugs are placed (under slight compression) in 22 mm
(inside diameter) by 10 cm long hexane-rinsed glass tubes. The glass tubes are
constructed from 22 mm (inside diameter) stock which has been tapered at one
end to facilitate attachment to the sampling pump. A teflon reducing adaptor
can also be fabricated which permits attachment to the sampling pump with no
modification to the glass tube. The cartridges are then placed in teflon
sealed 38 mm x 200 mm culture tubes wrapped with aluminum foil to protect the
sampling cartridges from ultraviolet light.
Any high-volume personnel sampling pump capable of maintaining a constant
flow rate of 3 to 4 liter/minute can be used. Samples are collected at this
nominal flow rate for between 8 to 12 hours allowing a total sample volume of
between 1 to 4 cubic meters (m3) .
Polyurethane foam has been shown to be excellent for trapping a wide
variety of semi volatile organic compounds in ambient air including numerous
chlorinated pest icides,23242526 polych lor i nated biphenyls (PCBs),24
polychlorinated naphtalenes,29 herbicides and their corresponding methyl
esters,25 27 organophosporus pest i c i des,24 25 ch I or i nated benzenes,25
chlorinated phenols,25 and polynuclear aromatic hydrocarbons.2328
Table 4-8 lists the representative components of the above compound classes
that have been collected in ambient air using this technique.
Uses
This procedure and modifications of this procedure have been used
successfully to collect airborne chlorinated organics including pesticides,
PCBs, and a variety of chlorinated benzenes and phenols and is generally
applicable to the measurement of such compounds in the ng/m3to ug/m3
range when sensitive analytical techniques are employed (GC/Electron
Capture). These methods are generally not applicable for the more volatile
organic compounds (those exhibiting a vapor pressure of greater than 1 mm (Hg)
4-48
-------
Sect i on 4.2,
Revision 0
Page 2 of 7
TABLE 4-8. ORGANIC COMPOUNDS COLLECTED IN AMBIENT AIR USING LOW
VOLUME OR HIGH VOLUME POLYURETHANE FOAM SAMPLERS
PoIychI orinated biphenyls
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1016
Aroclor 1248
Aroclor 1254
Aroclor 1260
Chlorinated pesticides
a ch lordane p,p1-DDT
ych lordane Endosulfan
Chlordance (technical) Heptachlor
Mi rex Aldrin
a BHC
p BHC
yBHC (I indane)
5 BHC
p,p1-DDD
p.p'-DDE
Po I ych lor i nated naphthalenes34
Halowax 1001
Halowax 1013
Chlorinated Benzenes 25 35 26 33
1,2,3-tr i chIorobenzene
1,2,3,4-tetrachIorobenzene
PentachIorobenzene
HexachIorobenzene
PentachIoron i trobenzene
Chlorinated phenols25
2,4,5-trichloro phenol
Pentachlorophenol
(continued)
4-49
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Section 4.2.8
Rev i s i on 0
Page 3 of 7
TABLE 4-8 (continued)
Herbicide Esters25
2,4-D Esters, isopropyl
2,4-D Esters, butyl
2,4-D Esters, isobutyl
2,4-D Esters, isoethyl
Organophosphorus pesticides
Mevinphos Ethyl parathion
Dichlorvas Parathion
Ronnel Ma lath ion
Chlorpyripos
Diazinon
Methyl parathion
Carbamate pesticides 25'32
Propoxur
Catbofuran
Bendiocarb
Mexacarbate
Carbaryl
Urea pesticides25
Monuron
Diuron
Linuron
Terbuthiuron
Fluometuron
Chlorotoluron
Triazine pesticides 25'32
Simazine
Atraz i ne
Propazine
(continued)
4-50
-------
Section 4.2,
Revision 0
Page 4 of 7
TABLE 4-8 (continued)
Pyreth r i n pest i c i des 25
Pyrethrin I
Pyrethrin I I
AIlethrin
d-Trans-allethrin
Dicrotophos
Resmethrin
Fenvalerate
Polynuclear aromatic hydrocarbons
Naphthalene
Biphenyl
Fluorene
Dibenzoth iophene
Phenanthrene
Anthracene
Carbazole
2-Methyl anthracene
1-Methyl phenanthrene
F luoranthene
Pyrene
Benzo (a) fluorene
Benzo (b) f luorene
Benzo (a) anthracene
Chrysene/tr i phenyIene
Benzo (b) fluoranthene
Benzo (e) pyrene
Benzo (a) pyrene
Perylene
o-Phenylenepyrene
Dibenzo (at/ah) anthracene
Benzo (g,h,i) perylene
Coronene
4-5I
-------
Section 4.2.8
Revision 0
Page 5 of 7
at 20°C) nor are they applicable for differentiating between vapor phase
organics and those adsorbed on particulate matter. When collection of such
compounds is desired, it wi I I be necessary to utilize separate collection media
(Tenax-GC, filters, etc.) or combination cartridges.
Although sampling trains consisting of a particulate pre-fi Iter followed
by a backup sorbent cartridge have been described,30 indications are that
large portions of the particulate associated organic compounds may volatilize
off the particulate and onto the backup sorbent during collection, giving
higher than actual vapor base measurements and lower than actual particulate
assoc i ated measu rements.50 45
The listing supplied in Table 4-8 will aid investigators in determining
the applicability of this sampling method to their particular application.
Potential users are cautioned that method validation studies for many of the
compounds listed, including determination of collection efficiencies,
resorption recoveries, etc., have not been conducted.
The investigator should keep in mind that the procedure described herein
is meant, in its broadest application, to be a screening technique and is
therefore necessarily general. If specific conditions, compounds of interest,
concentrations, detection requirements, etc. are known, such factors should be
carefully considered and the appropriate literature sources reviewed to
optimize procedures relevant to specific needs. For instance, use of a
cartridge composed of a PUF/adsorbent resin "sandwich" has been described by
Lewis and McLeod which may be useful in collecting compounds with low PUF
breakthrough volumes.25
Procedures for Use
1. Calibrate the sampling pump as per the procedure outlined in Method
IV-7. Adjust pumps to a target flow rate of 3 to 4 I iters/minute.
2, Sampling procedures.
a, Assemble sampling train (see Figure 4-4). Set train up at
desired location and hang sampler on a tripod, music stand, or
similar device. To insure stability in wind gusts, weighting of
these devices or some method of anchoring is advisable. The
use of wooden or other nonsparking stakes can be used, but
experience has shown these to be less convenient and often
more work than weighted stands.
b. Record all initial information (time, counter reading, cartridge
number, pump number, sampler, blank number, barometric pressure,
ambient temperature, relative humidity, etc.).
c, Start pump and observe system to determine if appropriate flow
rate is being maintained. For systems utilizing rotameters the
calibrated rotameter setting should be maintained during the
4-52
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Sect i on 4.2,
Rev i s i on 0
Page 6 of 7
TUBING
PARTICULATE FILTER
(OPTIONAL)
MOISTURE TRAP
(OPTIONAL)
PUMP
PYREX TUBE
PREFILTER OR PACKING
POLYURETHANE FOAM SORBENT PLUG
TRIPOD,
ADJUSTABLE
HEIGHT
Figure 4-4. PUF sampling train schematic.
4-53
-------
Sources
Section 4.2.8
Rev i s i on 0
Page 7 of 7
entire run and should be monitored regularly. Any adjustments
to the rotameter are made by opening or closing the needle
valve and should be noted in the field log. Most constant flow
sampling pumps have low-flow indicators and/or an automatic
shut-off feature at low-flow conditions. These should be
initially observed and periodically monitored during the course
of samp I ing.
Allow pump to run for desired sampling time.
At end of sampling period, observe rotameter level or low flow
indicator to determine if flow rate has been maintained. Shut
down sampling pump and record all pertinent information (counter
reading, time, barometric pressure, relative humidity, ambient
temperature, problems, comments, etc.). The final flow rate
should not deviate from the initial flow rate by more than ± 5%.
Remove PUF cartridge (use clean gloves) and wrap it
hexane-rinsed aluminum foil.
with
Place foil-covered cartridge in a hexane-rinsed glass bottle or
culture tube that has been properly labeled. Plugs of glass
wool are placed below and above the cartridge and the tube is
tightly capped. The tube should be gently shaken to insure that
the cartridge does not rattle inside the culture tube.
Place sample identification tag on sample bottle or culture tube
and fill out chain of custody form.
Calculate total sample volume at standard conditions as in
Method IV-7.
GCA Corporation. "Qua
Samp I i ng Procedures."
ity Assurance Plan, Love Cana
EPA Contract 68-02-3168.
Study, Appendix A,
Lewis, Robert G. and MacLeod, Kathryn E. "Portable Sampler for Pesticides
and Semi volatile Industrial Organic Chemicals in Air." Analytical
Chemistry, Volume 54, pp. 310-315, 1982.
GCA Corporation. "Guidelines for Air Monitoring at Hazardous Waste Sites
for Volatile and Semi volatile Organic Compounds Using Tenax and
Polyurethane Foam Sorbents." EPA Contract 68-02-3168, April 1983.
4-54
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Section 4.2.9
Revision 0
Page 1 of 6
4.2.9 METHOD IV-9: DETERMINATION OF TOTAL SUSPENDED PARTICULATE IN AMBIENT
AIR USING HIGH-VOLUME SAMPLING TECHNIQUE
Description
Ambient air is drawn into a covered housing and through a filter by means
of a high-volume blower at flow rates between 1.13 to 1.70 mVmin (40 to 60
ftVmin). Particles within the size range of 100 to 0.1 urn diameter are
collected on the filter although sampler flow rate and geometry tends to favor
particles less than 60 urn aerodynamic diameter. The mass concentration of
suspended particulate is computed by measuring the mass of collected
particulate (gravimetric analysis) and the volume of air sampled.
High volume ambient air samplers (Figures 4-5 and 4-6) are readily
available from a number of vendors and should meet the specifications described
in 40 CFR Part 50 Appendix B--Reference Method for the Determination of
Suspended Particulate in the Atmosphere (High Volume Method) .37 Fi Iter media
(glass fiber filters) with a collection efficiency of at least 99 percent for
particles of 0.3 urn diameter are also specified for use. Other types of filter
media (e.g., paper) or specially prepared filters may be desired in instances
where specific analysis is contemplated or low background levels of certain
poI Iutants i s des i red.
After sample collection, pretared filters are analyzed gravimetrically
to determine the total particulate loading. Trace metal analyses may be
accomplished by extracting all or part of the filter and analyzing the extract
accordingly (i.e., atomic absorption, ICP). It should be noted that when trace
metal analysis is desired, it is extremely important to submit blank filters
from each lot to the laboratory to determine background concentrations.
Modified high-volume sampling techniques have also been used to
efficiently collect certain organic compounds. Stratton, et a I.,31 and
Jackson and Lewis38 describe samplers modified to include a throat extension
between the filter housing and blower that contains polyurethane foam sorbent.
This arrangement can also be used to trap polynuclear aromatic hydrocarbon
(PNAs). Additional sorbents or combinations can be used dependent upon
specific collection requirements. As with trace metal analysis, it is
important that blank filters and sorbents be submitted to the laboratory to
determine the existence of background concentrations.
The described procedures can be used to collect Total Suspended
Particulate (TSP) matter in ambient air. The collected material may be
extracted and analyzed for trace metals or particulate related organics of
low volati I ity. In the latter case, backup collection techniques (PUF)
would be advisable.
4-55
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Section 4.2.9
Revision 0
Page 2 of 6
RETAINING
RING
ADAPTER
GASKET
BOLT i
"BACK GROMMET
ADAPTER
JNTING
PLATE
MOUNTING^*,.
: \
RING
- WIRE
CORD
TUBING
#
^
NUT a BOLT
ROTAMETER ft
V
CONDENSER
AND CLIP
[ BACKING
PLATE
Source: Reference 37.
Figure 4-5. Exploded view of typical high-volume air sampler parts.
Source: Reference 37.
Figure 4-6. Assembled sampler and shelter.
4-56
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Section 4.2.9
Rev i s i on 0
Page 3 of 6
Procedure for Use
1, CaI ibrat ion
Refer to 40 CFR 50, Appendix B, Part 8.0--Cal i brat ion as
amended37 and the EPA Proposed Changes to Ambient Measurement
Methodology for Carbon Monoxide, Particulate, Sulfur Dioxide, 47 FR
2341, January 15, 1982.35
Essentially, samplers must be calibrated when first purchased, after
major maintenance on the sampler (e.g., replacement of motor or
brushes), any time the flow measuring device (rotameter or recorder)
has been replaced or repaired, or any time a one-point calibration
check deviates from the calibration curve by more than ±6 percent.
The following procedure is based on the use of a certified variable
resistance orifice as the sampler calibration device and a continuous
flow-rate recorder (Dickson recorder) used to ensure the accuracy of
air volume measurements. Samplers may also be equipped with an
electronic flow controlling mechanism to perform the same function.
Flow-rate controllers and recorders are not as yet required;
however, errors resulting from nonconstant flow rates can be greatly
reduced by using such devices. In addition, the currently approved
flow indicators (rotameters) have been shown to be subject to a
variety of errors caused by physical damage, dirt deposition, and
flow restrictions in connecting tubing.
a, Remove filter retaining plate from the sampler to be calibrated
and place a clean filter in the filter holder.
b, Attach the variable resistance orifice (VRO) to the sampler and
position the orifice setting to full open. Secure the VRO fall
plate to insure an air tight seal with the orifice gasket.
Attach a slack tube manometer to the sampler unit.
c, Plug sampler into 120-volt source, while checking manometer to
insure that the orifice pressure drop does not exceed the range
of the manometer. Let the sampler run for about 5 minutes.
d, Turn motor off and place a fresh chart on the unit. The chart
should include the following information: high-volume sampler
identification, date and time of calibration, and operator's
name. The chart should be labeled "Calibration Data."
e, Check the recorder for proper operation, and zero the pen if
necessary.
f, Determine five approximately equally spaced intermediate points
which provide pressure drops between the desired maximum and
minimum operating point and record the following data on the
calibration sheet: 4.57
-------
Section 4.2.9
Revision 0
Page 4 of 6
pressure drop from the manometer (in. H20)
flow rate indicated on Dickson recorder, liters/mm
(ftVmin) .
Repeat three points centralized in the vicinity of the expected
sampler flow rate to insure accuracy in the field.
(The Dickson Recorder should be tapped gently prior to reading, to
insure that the recorder pen is in its final position.)
Record the airflow rate from the VRO high-volume calibration curve
for each flow recorder reading.
ACCEPTABILITY = 100
(Qo-Qc)| within 5%
Qc
where: Qo = observed flow rate
Qc = flow rate from calibrated curve
If the air flow rate exceeds the acceptable limits, rerun points for
which percent deviation exceeds 5 percent until acceptance limits are
attained.
Correct the sample flow rate to standard conditions using the
following formula:
where: Q2 = corrected flow rate std. liters/min
(std. ftVmin)
Q1 = recorded flow rate from chart,
I i ters/mi n (ftVmi n) .
T, = temperature during calibration, °K (°R).
T2 = standard temperature, 298°K (537°R).
P., = atmospheric pressure during calibration,
mmHg (in. Hg).
P2 = standard absolute pressure, 760 mmHg
29.92 in. Hg).
4-58
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Section 4.2.9
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Sample Col lection
Total suspended participate measurements are normally collected over
a 24-hour sampling period; however, this requirement may be altered
for hazardous waste sampling applications. Monitoring objectives
may require sampling at specific time intervals only (e.g., during
drum excavations), and high particulate loadings due to. heavy
equipment traffic may also require shortened sampling periods.
Sampling time selection will therefore be site specific and
obviously dependent upon a number of unique factors.
a, Installation of Clean Filter
(1) Remove faceplate by loosening the four wing nuts and
rotating the bolts outward.
(2) Obtain a clean, weighed filter and record the filter
number, high-volume sampler serial number, flowmeter
serial number, location, run date, and start time on the
data sheet.
(3) Carefully place the clean filter rough side up, on the
wire screen, and center the fi Iter so that when the
faceplate is in position, the gasket will form a tight
seal on the outside edge of the fi Iter.
(4) Replace faceplate, being careful not to move the filter,
and tighten the wing nuts evenly until the gasket forms an
airtight seal against the filter.
b, Operation Checks
(1) AI low sampler motor to warm up at least 5 minutes to reach
normal operating temperature.
(2) Assure that the flow recorder is connected to the sampler
using the same tubing as was used to cal ibrate the sampler.
(3) Place a new chart on the recorder and set at correct start
time.
(4) Record "Run Start" time and date, site identification, and
sampler number on the chart.
(5) Turn sampler off and set clock switch to desired setting.
Total suspended particulate samples are normally collected
over a 24-hour period; however, this requirement may be
altered depending on monitoring applications.
4-59
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Section 4.2.9
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Removing Exposed Filter
(1) Turn sampler "on" and allow to warm up at least 5 minutes.
(2) Check flow recorder chart for proper operation.
(3) Turn sampler "off" and record elapsed time in logbook and on the
data sheet.
(4) Remove chart and place in envelope.
(5) Carefully loosen wing nuts and remove faceplate gasket.
(6) Remove the exposed filter by gently grasping the ends of
the filter and lifting it from the screen. Fold the
filter lengthwise at the middle with the exposed side
"in." If the collected sample is not centered on the
filter, fold the filter accordingly so that sample touches
sample only.
(7) Place the filter in a glassine envelope, and place
glassine envelope with data sheet in a folder for return
to sample bank.
(8) Visually inspect for signs of leakage, damage, etc., to
the sampler and repair if necessary.
Sources
United States Environmental Protection Agency. "Appendix B--Reference
Method for the Determination of Suspended Particulate in the Atmosphere
(High Volume Method)". 40 CFR Part 50. November 25, 1971.
United States Environmental Protection Agency. "Proposed Changes to
Ambient Measurement Methodology for Carbon Monoxide, Particulate and
Sulfur Dioxide." 47 CFR 2341. January 15, 1982.
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4.3 SOIL GASES AND VAPORS
Monitoring of soil gases can often serve as a quick method of determining
the extent of pollutant migration or establishing perimeters of a site
containing buried wastes. Soil-gas exchange with the ambient atmosphere
greatly dilutes gaseous components making them difficult to detect.
Therefore, sampling in the soil can provide a more concentrated source for
underground waste detection. Soil-gas sampling also has particular
applicability to the identification of methane fluxes at sanitary landfills.
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4.3.1 METHOD IV-10: MONITORING GAS AND VAPORS FROM TEST HOLE
Discussion
Gas samples can be withdrawn from test holes by using a nonsparking
probe, brass and Teflon being the most suitable. The probe is then attached
to the gas inlet of the desired gas monitor such as those described in the
ambient gases section and Method IV-1 through IV-8. The test holes are easily
prepared by driving a metal rod (approximately 1 in. diameter) into the soil
with a drive weight. Commercial bar hole-makers are available that combine the
steel hole-making bar and drive weight into one unit (see Figure 4-7).3g
Uses
This system is particularly adapted for rapid evaluation of waste sites
for soil gas generation. When used in conjunction with a hydrocarbon analyzer
or an explosimeter it can rapidly determine the area I extent of a waste site or
the location of a particular emission source. It is recommended that the test
area be screened with a metal detector before sampling.
Procedures for Use
1. Select location free from rocks and debris. Screen location with
metal detector to varify absence of drums and pipes.
2, Place bar point on ground and raise drive weight, then allow weight
to fall on bar. It is only necessary to guide the weight in its
verticaI travel.
3. Continue until desired depth or any penetration resistance is reached.
4, Remove bar hole-maker.
5, Attach suitable length of Teflon tubing (stainless steel or brass may
be used in some instances but may result in some gas adsorption/
absorption) to monitor instrument gas inlet.
6. Lower tubing into test hole and operate monitor or gas sampling
device as listed in Methods IV-1 through IV-8.
7, Record results.
8. Remove sample tubing and observe that instrument readings return to
background. If not, change tubing before proceeding to next test
location.
9. Tramp over and recover test hole.
Sources
Flower, F.B. "Case History of Landfill Gas Movement Through Soils."
Rutgers University, New Brunswick, New Jersey.
4-62
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60cm
6cm
Section 4. 3.1
Rev i s i on 0
Page 2 of 2
1
1
-
1
_ -J
1
DRIVE WEIGHT
STEEL BAR {»l.2cm OD x IQOcm)
V
Figure 4-7. Bar hole-maker.
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Section 4.3.2
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4.3.2 METHOD IV-11: MONITORING GAS AND VAPORS FROM WELLS
Discussion
The sampling of wells for gases and vapors can be accomplished by
lowering an intake probe through a sealed cap on the top of the well,
(Figure 4-8). The intake probe should be of a nonsparking material that
will further minimize adsorption or resorption effects. Teflon or glass are
preferable to steel or brass in this application. The intake probe is then
connected to the desired gas monitor such as those described in the ambient
gases section and Methods IV-1 through IV-8.
Uses
Existing groundwater monitoring wells can be used to check for the
presence of those gases volatilized or otherwise liberated from the
groundwater. In some cases, the groundwater level will be below the top of
the screened portion of the-well allowing free soil gases to enter the well
casing.
Wells especially designed for soil-gas monitoring can also be placed by
conventional well placement techniques. The well casing, however, is
perforated the entire distance, the annular space is packed with gravel, and
the top is sealed with a grout cap.40The top of the casing can even be
equipped with a sampling valve to allow easy coupling to the monitoring
instruments.
Procedures for Use
1, Sound the well for water level or bottom.
2, Select the required length of Teflon tubing. It should be of
sufficient length to approach the water level or well bottom, but
not so long as to allow water or bottom sediments to enter probe
inlet. An inside diameter of 1/8 inch is usually sufficient.
However, because this size lacks rigidity, a small weight can be
secured to the inlet end to facilitate placement.
3, Lower the tubing through an appropriate sized stopper on the top of
the well casing. A wooden plug serves well. It is not critical to
maintain an effective seal around the tubing.
4. Lower intake to near bottom and attach outlet to monitor inlet.
5, Proceed with instrument operation according to Methods IV-1 through
IV-8 or the instrument operator's manual. Note: When using an
adsorption technique for qualification/quantification, Sisk4
recommends a sample rate of 1 Ipm for 5 to 30 minutes through Tenax
GC (see Method IV-7).
4-64
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Sect i on 4.3.2
Rev i s i on 0
Page 2 of 3
1
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V.';|
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s
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S
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r.ii
. « *
r *
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u* !'
i'- '. '.
AV-
Hv
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GAS SAMPLING VALVES
^ METAL CAP
^-CEMENT GROUT CAP
.-GRAVEL PACKING
GAS COLLECTION
PORT
Source: Reference 40.
Figure 4-8. Gas sampling we I
4-65
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Sect i on 4.3.2
Revision 0
Page 3 of 3
6, Gradually raise the intake tubing while observing the instrument
readings.
7. Record readings, then remove probe and close casing.
8, If instrument fails to return to background level, replace sample
inlet tube before Proceeding to next well. Note: Sometimes vapors
may condense on the lower portion of the sample tube, merely cutting
off the bottom several centimeters of the intake tube may remove the
source of contamination and allow reuse of the remaining sample tube.
Sources
Hatayama, H.R. "Special Sampling Techniques Used for Investigating
Uncontrolled Hazardous Waste Sites in California." In: National
Conference on Management of Uncontrolled Hazardous Waste Sites.
Hazardous Material Control Research Institute, Silver Springs, Maryland.
1981.
4-66
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Section 4.4
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Page 1 of 1
4.4 HEADSPACE GASES
Headspace gases are the accumulated gaseous components found above solid
or liquid layers in closed vessels. These gases may be the result of
volatilization, degradation, or chemical reaction. Poorly ventilated or
partially sealed areas can also act to concentrate gas vapors. Component
concentrations normally exceed those found in ambient measurements.
Therefore, the previously described ambient methods must be modified for
handling these higher concentrations and for the remote sensing of container
contents. The anticipated higher concentrations can be dealt with by altering
the instrument detector range, reducing the sample gas flow rate into the
instrument, or utilizing a sample dilution system. These techniques are
necessary for the prevention of saturation, poisoning, and/or gross
deterioration of the detector element. When lengthy extensions are used, one
must also take into account increased time lags for instrument response.
Most ambient measurement devices have sample intakes which are highly
directional and local ized. The use of an extension wi I I a I low the operator to
obtain samples from varying depths and distances within containers while
maintaining a safe position.
Headspace gases are often found in certain types of containers. Bulging,
stainless steel, lined, or other special designated drums are more likely to
contain hazardous headspace gases. A preliminary scan of the external seams,
edges, or any corroded areas with a vapor analyzer may indicate the nature of
the contents.
Poorly venti lated vessels can usually be sampled for headspace gases
through small hatches or openings. Fully sealed vessels must be approached
more cautiously since breach ing-may result in the uncontrolled release of
pressurized gases or the potential for violent reactions with the ambient
atmosphere. Any decision to open a sealed vessel should be based on sound
need and the investigator must be cognizant of the inherent dangers, and take
appropriate safety precautions.
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4.4.1 METHOD IV-12: SAMPLING OF HEADSPACE GASES IN SEMI SEALED VESSELS
Discussion
Sampling of headspace gases involves merely extending the intake or
otherwise conducting the contained gas to the detection device. Any of the
procedures discussed in the ambient section (Methods IV-1 through IV-8) can be
employed. The use of Teflon tubing of approximately 4.8 or 6.4 mm (3/16 or 1/4
inch) inside diameter works well as a probe extension.
Uses
This system is viable in a wide variety of appl icat ions. It is simple,
and only requires some adaption to match the extension tubing to the instrument
intake. The likelihood of high concentrations of contaminants is, however,
greater in contained vessels and, as a result, there is the potential for
detector saturation and fouling. It is advisable to place any instruments used
in this role in their highest operating range. Flame ionization detectors that
utilize the sample gas stream as their combustion air may have insufficient
oxygen for combustion and will likely require use of a dilution probe. The
introduction of entrained droplets from the container contents should also be
avoided. Careful handling of the extension tube to avoid close contact with
the materials surface and-in some instances the use of a glass wool filter plug
will prevent material buildup in the probe and detector.
Procedures for Use
1. Select an appropriate monitoring instument or device that will
characterize the gas if present. A combustible gas detector,
hydrocarbon vapor analyzer or stain detector tube is normally used.
Be particularly aware of the limitations of the instrument in use.
2, Attach the proper size and length tubing that will reach into the
container. The tubing seal with the monitoring instrument should be
leak tight.
3, Insert tubing into container or vessel opening and operate
instrument as per Methods IV-1 through IV-8 and the appropriate
operators manuaI.
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4.4.2 METHOD IV-13: SAMPLING OF HEADSPACE GASES IN SEALED VESSELS
Discussion
Sealed vessels, especially 55-gallon drums, present problems when
sampling for entrapped gases. The container must be opened to accept a sample
probe while still preventing uncontrolled release of its potentially hazardous
contents. Further, this must be accomplished while still protecting the
safety of the inspector.
On large vessels and tanks inspection valves and petcocks are normally
available. Sealed drums, however, are not designed to contain gases that
often develop as reaction products of the contents and have no such provisions.
Leak-free sample tops can be installed on these drums by attaching a
mechanism that wi I I dri I I through a leak-tight fitting strapped to the drum
(Figure 4-9). The system consists of a battery operated drill with a remote
control switch. The drill is mounted on a simple spring-controlled frame
which guides the drill bit through a Swage I ok cross fitting. The Swage I ok
cross is attached to a ball valve which, in turn, is attached to a mounting
plate. The mounting plate underside is gasketed with closed cell Neoprene
foam. The mounting plate is held against the container using standard steel
packaging straps. The cross fitting contains a Teflon seal which allows the
drill bit to rotate without allowing gases from the container to escape during
drum penetration. A pressure gauge is attached to one side of the Swage I ok
cross while a needle valve is attached to the side opposite the gauge. The
pressure gauge permits the waste handler to observe the internal pressure of
the container while the valve permits the removal of sample gas for analysis.
The valve and pressure gauge can also be used to insure pressure equalization
prior to further opening of the container. A light is located on the remote
control switch which indicates when the drum has been pierced. The electrical
control system is interlocked so that drill operation automatically stops upon
penetration of the container by the drill bit. The whole assembly is
activated remotely. Once the bit has penetrated the drum, contained gases
flow between the dri I I bit and the inside of the fittings. Release of the
gases is controlled by a needle valve. After sampling, the drill mechanism is
pulled away from the container until the drill bit clears the ball valve. The
ball valve is then closed, and the piercing mechanism up to the ball valve is
removed from the container. The ball valve and mounting plate are left intact
to serve as a permanent seal for the opening.
The monitors and detectors described in the Ambient Section (Methods IV-1
through IV-8) can then be adapted to the needle valve and the gas directed to
the instrument.
Uses
This device has been used on 55-gallon drums but would also be applicable
to other size drums and vessels. Fabrication specifications for this device
are found in Appendix B.
4-69
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Sect i on 4.4.2
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Page 2 of 4
CUT-OFF
SWITCH
BALL
VALVE
Source: Reference 41.
Figure 4-9. Drilling mechanism.
4-70
SPRING
LOADING
DEPTH STOP
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Sect i on 4.4.2
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Page 3 of 4
Procedures for Use
1. Assemble the drill assembly as per Appendix B - Equipment
Ava i Iab i I i ty and Fabr i cat i on.
2, Brush clear any loose rust or dirt to assure a leak-free seal. Seat
assembly against the drum side. Tighten mounting straps using
portable packaging equipment.
3, Assure that all fittings are snug and needle valve is fully closed.
4. DepIoy remote controI cab Ie to fu I I extent and stand beh i nd safety
screen.
5, Activate dri I I.
6. After penetration is indicated by light on remote control unit,
approach container while monitoring internal drum pressure with
pressure gauge on sampler.
7, Attach desired monitor instrument for container content
characterization. Any device listed in the ambient section can be
employed (Method IV-1 through IV-8). The instrument can be attached
by using an appropriate size Teflon tubing (see Method IV-11).
After sampling, close needle valve. Extra caution is necessary for
highly pressurized containers, as most menitors are designed to
accept ambient pressure gases.
8, After proper quantification and/or identification of the contained
gas, the safety officer should decide whether the gas can be vented
or should be properly contained for later disposal.
9, The fulI assembly can be removed if the gas has been properly vented
or disposed of; otherwise the drill can be loosened from the bit and
removed from the guide assembly as outlined below.
a, Pull drilling mechanism away from container until the drill bit
clears the ball valve. Close ball valve.
b, Loosen nut containing Teflon seal.
c, Unscrew bolts, holding drill assembly to mounting plate.
d, Remove drill assembly from mounting plate pulling drill bit
through Teflon seal .
e, Remove cross fitting as unit from ball valve.
The remaining mounting plate and ball valve serve as a permanent
seal until the container can be disposed of properly.
4-7I
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Section 4.4.2
Rev i s i on 0
Page 4 of 4
Sources
Snyder, Roger, Tonkin, Martha E., McKissick, Alton M., "Development of
Hazardous/Toxic Wastes Analytical Screening Procedures," Atlantic
Research Corporation, July 1980.
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Section 4.5
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Page 1 of 4
4.5 REFERENCES
1. Spittler, T. M., and A. W. Oi. Ambient Monitoring for Specific
Volatile Organics Using a Sensitive Portable PID GC. In: National
Conference on Management of Uncontrolled Hazardous Waste Sites.
Washington, DC. October 28-30, 1981.
2, U.S. Department of Health, Education and Welfare. NIOSH Manual of
Analytical Methods, Volumes 1-7. DHEW-NIOSH Publication No. 79-141,
August 1979.
3, Spittler, T. M., and A. W. Oi. Ambient Monitoring for Specific
Volatile Organics Using a Sensitive Portable PID GC. Management of
Uncontrolled Hazardous Waste Sites, Washington DC. October 1981.
4, Ecology and Environment, Inc. Field Investigations of Uncontrolled
Hazardous Waste Sites, FIT Project, FIT Operation and Field Manual.
1982.
5, Barker, N. J. and R. C. Levenson. A Portable Photoionization GC for
Direct Air Analysis. American Laboratory, December 1980.
6, Linenberg, A. Automated On Site G. C. Measurements of Vapors In the
Atmopshere. Sentex Marketing Material, Ridgefield, New Jersey, May
1983.
7, Schlitt, H., H. Knoeppel, B. Versino, A. Peel, H. Schanenburg, and
H. Vissers. Organics in Air: Sampling and Identification. In:
Sampling and Analysis of Toxic Organics in the Atmosphere. ASTM STP
721. American Society for Testing and Materials. Philadelphia,
Pennsylvania, 1980. pp. 22-35.
8, McMillan, C. R., J. Brooks, D. S. West, N. F. Hodgson, and J. D.
Mulik. Development of a Portable Multiple Sorbent Ambient Air
Sampler. In: National Symposium on Monitoring Hazardous Organic
Pollutants in Air. Raleigh, N.C. April 28 to May 1, 1981.
9, Gallant, R. F., J. W. King, P. L. Levins, and J. F. Pucewicz.
Characterization of Sorbent Resins for Use in Environmental
Sampling. EPA-600/7-78-054, March 1978.
10. Pucewicz, J. F., J. C. Harris, and P. L. Levins. Further
Characterization of Sorbents for Environmental Sampling.
EPA-600/7-79-216. September 1979.
11. U.S. Environmental Protection Agency. Selection and Evaluation of
Sorbent Resins for the Collection of Organic Compounds.
EPA-600/7-78-054. March 1978.
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12, GCA Corporation, "Guidelines for Air Monitoring at Hazardous Waste
Sites for Volatile and Semi-Volati le Organic Compounds using Tenax
and Polyurethane Foam Sorbents," Contract No. 68-02-3168, April 1983.
13. Walling, J. F. and T. A. Hartlage, "Standard Operating Procedure for
Sampling Gaseous Organic Air Pollutants for Quantitative Analysis
using Tenax," EMSL/RTP-SOP-EMD-18, Revision 0, February 1982.
14, Berkley, R., J. Bumgarner, D. Driscoll, C. Morris, L. Wright,
"Standard Operating Procedure for the GC/MS Determination of
Volatile Organic Compounds Collected on Tenax-GC Sorbent Cartridges
(Semi-Automated Data Processing)" EMSL/RTP-SOP-EMD-014, Revision 1,
August 1982.
15, GCA Corporation. Quality Assurance Plan, Love Canal Study, Appendix
A, Sampling Procedures. EPA Contract 68-02-3168.
16. GCA Corporation. Quality Assurance Plan, Love Canal Study, Appendix
B, Laboratory Procedures. EPA Contract 68-02-3168.
17. Pellizzari, E. D., B. H. Carpenter, J. E. Bunch, and E. Sawicki .
Collection and Analysis of Trace Organic Vapor Pollutants in Ambient
Atmospheres. Environmental Science and Technology 9:556, 1975.
18, Pellizzari, E. D., J. E. Bunch, R. E. Berkindey, and J. McRay.
Collection and Analysis of Trace Organic Vapor Pollutants in Ambient
Atmospheres: The Performance of a Tenax-GC Cartridge Sampler for
Hazardous Vapors. Anal. Letters. 9:45-63, 1976.
19, Jonsson, A. and S. Berg. Determination of 1,2-Dibromoethane,
1,2-Dichloroethane and Benzene in Ambient Air Using Porous Polymer
Traps and Gas Chromatographic-Mass Spectrometric Analysis with
Selected Ion Monitoring. J. Chromatogr. 190:96-106, 1980.
20. Janek, J., J. Ruzickova, and J. Novak. Effect of Water Vapor in the
Quantitat ion of Trace Components Concentrated by Frontal Gas
Chromatography on Tenax-GC. J. Chromatogr. 99:689-696, 1974.
21. Russel, J. W. Analysis of Air Pollutants Using Sampling Tubes and
Gas Chromatography. Environ. Sci. Techno I. 9:1175, 1975.
23. Biddleman, T. F. Inter laboratory Analysis of High Molecular Weight
Organochlorines in Ambient Air. Atmos. Environ. 15:619-624, 1980.
24. Lewis, R. G., A. R. Brown, and M. D. Jackson. Evaluations of
Polyurethane Foam for Sampling of Pesticides, Polychlorinated
Biphenyls, and Polychlorinated Naphthalenes in Ambient Air. Anal.
Chem. 49:1668-1672, 1977.
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25. Lewis, R. G., and K. E. McLeod. Portable Sampler for Pesticides and
Semivolati le Industrial Organic Chemicals in Air. Anal. Chem.
54:310-315, 1982.
26. Billings, W. N., and T. F. Biddleman. Field Comparison of
Polyurethane Foam and Tenax-GC Resin for High Volume Air Sampling of
Chlorinated Hydrocarbons. Environ. Sci . and Techn. 14:679-683,
1980.
27. Grover, R., and L. A. Kerr. Evaluation of Polyurethane Foam as a
Trapping Medium for Herbicide Vapor in Air Monitoring and Worker
Inhalation Studies. J. Environ. Sci. Health. B16: 59-66, 1981.
28. Lindgren, J. L., H. J. Krauss, and M. A. Fox. A Comparison of Two
Techniques for the Collection and Analysis of Polynuclear Aromatic
Compounds in Ambient Air. J. Air Poll. Control. 30:166-168, 1980.
29, Hunt, G. T., N. Pangaro, G. A. Sotolongo, "Ambient Monitoring of
Polynuclear Aromatic Hydrocarbons Employing High Volume Polyurethane
Foam Samplers," presented at the Eighth International Symposium on
Polynuclear Aromatic Hydrocarbons, Columbus, OH, October 26-28, 1983.
30. Keller, C. and T. F. Bidleman, "Collection of Vapor Phase Polycyclic
Aromatic Hydrocarbons in Ambient Air," Paper Presented Before the
Division of Environmental Chemistry, American Chemical Society,
Kansas City, MO, 1982.
31. Stratton, C. L., S. A. Whit lock, and J. M. Allan. A Method for the
Sampling and Analysis of Polychlorinated Biphenyls (PCBs) in Ambient
Air. EPA-600/4-78-048, August 1978.
32. Rhoades, J. W. and D. E. Johnson, "Evaluation of Collection Media
for Low Levels of Airborne Pesticides," EPA-600/I-77-050, 1977.
33. Billings, W. N. and T. F. Bidleman, "High Volume Collection of
Chlorinated Hydrocarbons in Urban Air Using Three Solid Adsorbents,"
Atmos. Environ. , H (2), 1983.
34. Lewis, R. G. and M. D. Jackson, "Modification and Evaluation of a
High Volume Air Sampler for Pesticides and Semi volatile Organic
Chemicals," Anal . Chem.. 54 (3), 1982.
35. Lewis, R. G., "Contractor Evaluation and Analysis of Air Samples from
the Love Canal Area for Pesticies and Semi-Volati le Chlorinated
Organics," HERL/RTP, NC, 1980.
36. Thrane, K. E. and A. Mikalsen, "High-Volume Sampling of Airborne
Polycyclic Aromatic Hydrocarbons Using Glass Fiber Filters and
Polyurethane Foam," Atmos. Env i ron. , 15 (6), 1981.
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Sect i on 4.5
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Page 4 of 4
37. Federal Register, Appendix B. Reference Method for the
Determination of Suspended Particulate in the Atmosphere (High
Volume Method). 40 CFR 50, 1971.
38. Jackson, M. D., and R. G. Lewis. Polyurethane Foam and Selected
Sorbents as Collection Media for Airborne Pesticides and
Polychlorinated Biphenyls. In: Sampling and Analysis of Toxic
Organics in the Atmosphere. ASTM STP 721. pp. 36-47, 1980.
39. Flower, F. B. Case History of Landfill Gas Movement through Soils.
n: The Proceedings of the Research Symposium "Gas and Leachate from
Landfills" at Cook College, Rutgers University, New Jersey, March 25
and 26, 1975. U.S. EPA 600/9-76-004. 1976. pp. 177-189.
40. Hatayama, J. R. Special Sampling Techniques Used for Investigating
Uncontrolled Hazardous Waste Sites in California. In: National
Conference on Management of Uncontrolled Hazardous Waste Sites.
Hazardous Materials Control Research Institute. Silver Springs,
Maryland. 1981.
41. Synder, R. E., M. E. Tonkin, A. M. McKissick, and M. Alton.
Development of Hazardous/Toxic Wastes Analytical Screening Procedures
- Part I. Atlantic Research Corporation, ADA-095-506. 1980.
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Section 5.1
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Page 1 of 2
SECTION 5.0
SIZING RADIATM
5.1 GENERAL
Radiation monitoring should be one of the first tasks performed when
initially approaching a waste site or hazardous material spill. This
requirement is dictated by the potential risk to human health on contact with
a radioactive source as exposure to even small amounts of energy may result in
marked biological damage.
Radiation monitoring for hazardous waste situations essentially involves
two approaches: personnel monitoring and survey monitoring. Personnel
monitoring uses instruments designed to measure total cumulative radiation
exposure which can be used to estimate the absorbed dose (in units of rad or
rem). The instruments are worn or carried directly by the personnel being
monitored and consist of such devices as film badges, thermoluminescent
dosimeters, self-read ing dosimeters, and pocket chambers. Survey instruments
are meant to measure ionizing radiation -- expressed as an air exposure
rate (in units of mi I I iroentgens/hr) or activity of the source expressed as
a disintegration rate (counts/minute). As do personnel monitors, these devices
rely on the ability of radiation to cause ionizations and consist of ionization
chambers, proportional counters, Geiger-Mueller instruments, and scintillation
devices. They are particularly useful in performing initial field surveys to
detect and locate the presence of radioactive sources and in drum screening
procedures performed prior to further drum handling (i.e., staging, sampling,
compositing, etc.).
Although all of these detection instruments rely on the ability of
radiation to cause ionization, each differs in its sensitivity, i.e., its
ability to detect different types and varying intensities of radiation.
Basically there are four main groups of ionizing radiation types. These
include:
heavy, positively charged particles such as alpha particles,
protons, deuterons, trit ions, and possibly mesons each of which
exhibit similar mechanisms of interaction with matter;
beta particles including both positrons and electrons;
electromagnetic radiation including x-ray and gamma
radiation; and
neutrons.
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For the purposes of this section, however, only alpha, beta and gamma
radiation will be discussed, as they are the types most likely to be
encountered at a hazardous waste site.
Alpha particles are characterized as a charged particle having two
protons and two neutrons and, due to this large mass and charge (in addition
to high velocity), have a high probability of interacting or colliding with
orbital electrons and atomic nuclei. They have a limited tissue penetration
ability, however, since this type of radiation tends to lose its energy over
short distances. It is therefore easy to shield against and poses little
threat outside of the human body. However, due to its high specific
ionization, alpha radiation is capable of totally destroying cellular material
if it is able to locate within the body (e.g., by ingest ion, inhalation, etc.).
Beta particles are negatively charged particles that can be construed as
high-speed electrons. In contrast with electrons, however, beta particles
orginate in the nucleus. They exhibit medium specific ionization and
penetration when compared to alpha particles. Although they pose a greater
external body threat than alpha, beta particles of low energy are usually
stopped by the horny dead layers of the skin. Beta particles with enough
energy to penetrate the basal layer of the epidermis, however, still pose an
external threat. They can be shielded by a few millimeters of aluminum and,
like alpha particles, generally present a greater threat if their source is
located inside the body.
Gamma radiation is a type of electromagnetic radiation of nuclear origin
with a zero rest mass and no charge. It has the lowest specific ionization of
the three classifications and possesses the ability to penetrate tissue for
great distances. It therefore constitutes the greatest external radiation
hazard (in comparison to alpha and beta) as it is capable of deep penetration
within the body and is a threat to all organs. For this reason gamma
radiation is the most routinely monitored radiation type at hazardous waste
sites and environmental spills.
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5.2 PERSONNEL MONITORS
Although no specific method is outlined in this manual for personnel
radiation monitors (this is best covered by individual manufacturer
instructions), it is important that their existence and basic characteristics
be mentioned in this section. For this reason, the three basic types of
personnel monitors, namely film badges, thermoluminescent dosimeters, and ion
chambers, will be discussed as to the specific characteristics and relative
advantages of each.
Film Badge
The use of films for monitoring personnel exposure is considered to be
the most practical, although least accurate, of the existing methods. The
method employs a gelatin base with a silver halide spread on film or glass.
Radiation interacts within the silver halide in the emulsion by means of
ionizations, thereby causing the formation of a latent image which, upon
development, is converted into a black deposit of metallic silver. This
darkening can then be related to the type, energy, and quantity of radiation
received by the film badge. It is capable of recording a permanent record of
personnel exposure.
Thermo luminescent Dosimeters
Thermo luminescent dosimeters (TLD) can replace film badges for most
applications. In general they are more sensitive and more accurate than film
badges and can be processed more quickly and less expensively. These devices
detect radiation by storing ionization energy in defects of the crystal I at ice
of certain doped solids, such as LiF (Mn) and Ca F2 (Mn). The altered
energy levels are read out by heating the solid which then releases visible
light. The light output is proportional to the absorbed radiation energy and
can be related to exposure or dose units. TLD's can be reused but do not
provide a permanent record of exposure because the information is erased upon
readout. A permanent record is kept in the form of the original glow curve
(light output vs. time (or temperature)) trace which can be stored on paper or
in electronic memory.
Self-Reading Dosimeter
A self-read ing dosimeter is essentially an ion chamber containing two
electrodes, one being a thin quartz loop free to move with respect to its
mounting and the other a fixed heavy quartz fiber. Like charges are placed on
both loops causing the movable one to be repelled from the fixed loop.
Ionization entering the chamber reduces the charge on the loops allowing the
movable one to return towards its neutral position, the distance being
proportional to the dose received in the chamber. The device also includes an
optical system and transparent scale which permits instant results at any time
without external readers. They are rugged, sensitive instruments small enough
to be worn comfortably and extremely useful for measuring integrated exposure
I eve Is.
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Pocket Chambers
A pocket ion chamber is basically a cylindrical electrode and a coaxial
collecting rod which is insulated from the rest of the device. A charge is
placed on the collecting rod, and this charge is subsequently reduced when
ions formed upon exposure to radiation collect on the rod. The main
disadvantage of the pocket chamber is that the col Iecting-rod charging
procedure and the determination of exposure must be accomplished externally on
a unit called a "charger-reader." The main advantages of pocket chambers, in
comparison to the direct-read ing dosimeter, are the low cost and simplicity.
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5.3 SURVEY INSTRUMENTS
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Radiation survey instruments must meet the same criteria as previously
outlined for other monitors used at hazardous waste sites. They should be
portable, rugged, sensitive, simple in design and operation, reliable, and
intrinsically safe for use in explosive atmospheres. No one survey instrument
or type of instrument can be expected to totally meet all of these criteria
and the investigator must be aware of the characteristics (and limitations)
of each type of detector.
It is of primary concern that the proper instruments are chosen for
the particular survey requirements. Radiation survey instruments are designed
to detect only certain types of radiation and only operate within certain
exposure rate ranges. In most cases, more than one kind of instrument will be
needed to insure that an area is free of radioactive sources or contamination.
An instrument sensitive to background levels of gamma radiation should be the
first one used. Scintillation detectors meet this requirement. Geiger-Mueller
detectors also meet this need and have the additional advantages of being
sensitive to beta radiation. Detection of alpha radiation requires another
instrument having a thin window detector. Either gas ionization or
scintillation principles may be employed in alpha detectors. This discussion
will be limited to ionization chambers, proportional counters, Geiger-Mueller
counters, and scintillation detectors.
Ionization Chambers
Ionization chambers are instruments in which the ionization initially
produced within the chamber by radiation is measured without further gas
amplification. It consists of a gas-filled envelope (usually air at
atmospheric pressure) with two electrodes at different electrical potentials.
The walls of the tube generally serve as the cathode and a wire mounted down
the center of the tube serves as the anode. Ionizing radiation entering the
chamber produces ions which migrate towards the electrode due to the applied
potential, producing a current. This current requires amplification to a
measurable level before it can be recorded on a meter. These are high-range
instruments (low sensitivity) and are used extensively for measuring high
intensity beta, gamma, or x-radiation. No aural indication is possible with
these instruments and operators must be constantly aware of the meter to
determine radiation intensity. Ionization chambers do not record individual
radiation particles but integrate all signals produced as an electric current
to drive the meter. They should be calibrated to the type and intensity of
radiation desired to be measured in mi I I iroentgens/hr (or roentgens/hr).
Proportional Counter
Instruments of this type derive their name due to their operation in the
proportional region of the gas ionization detector response curve. Instrument
probes have an extremely thin window that allows alpha particles to enter and
as such are used extensively for this purpose by adjusting instrument
operating parameters to discriminate against beta and gamma radiation. The
meter is read in counts per minute and usually has several sensitivity
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scales. It should be noted that due to the nature of alpha particles, it is
important to hold the probe as close as possible to (though not in contact
with) the surface being monitored. The window of the proportional counter is
delicate in construction therefore requires care when using as a field
instrument.
Geiaer-Mueller Counter
These instruments operate principally in the same manner as ionization
chambers except that secondary electrons are formed allowing for greater
sensitivity. The chambers are filled with an inert gas such as argon, helium,
or neon (below atmospheric pressure) and a quench ing-gas which functions to
control the secondary electron formation. These instruments are very
sensitive and are commonly used to detect low level gamma and/or beta
radiation. Meters are read in counts/minute or mi I I iroentgens/hour. The gas
amplification process inherent in this type of detector allows a single beta
particle or gamma photon to be detected. It should be noted that these
devices are sensitive instruments and care should be taken not to exceed their
maximum capacity to prevent damage to the GM tube.
Sc i nt i I I at i on Detectors
These devices depend upon light produced when ionizing radiation
interacts with a media (solid crystal used in survey instruments). The
produced flashes of light or scintillations fall onto a photomultipl ier tube
which converts them to electrical impulses. These impulses are amplified and
subsequently measured to give an indication of the level of radiation
present. These are extremely sensitive instruments used to detect alpha,
beta, or gamma radiation simply by choosing the correct crystal. Alpha
particles are detected with a silver activated zinc sulfide screen, beta
radiation with an anthracene crystal (covered with a thin metal foil to screen
alpha particles), and gamma or x-ray with a sodium iodide crystal. The
instrument can be calibrated in the same manner as for ion chambers and Geiger-
Mueller instruments. The operator should keep in mind that in older models the
photomultipl ier tube may be damaged if directly exposed to light without first
disconnecting the voltage.
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5.3.1 METHOD V-1 : RADIATION SURVEY INSTRUMENTS
Discussion
As previously noted, a variety of radiation survey instrumentation
exists, each capable of responding to different types and levels of ionizing
radiation. The procedure delineated below is therefore purposely general and
simply outlines common instrument features and operational steps. It is by no
means meant to replace the instrument instruction manual but is only meant to
serve as a supplemental guide.
Radiation survey instruments are used to detect the presence of
radioactive sources. They are useful when making decisions concerning personal
safety, determining levels of contamination, and meeting transportation and
d i sposaI requ i rements.
Procedures for Use
1. Choose an instrument or interchangeable detector tube which is
consistent with the investigative requirements.
2, Turn selector switch to the standby or the warm-up position and
allow instrument to warm-up for 1-2 minutes.
3, Turn instrument selector switch to battery check position and check
battery strength.
4. Turn range selector switch to appropriate scale factor (e.g., IOOX,
10X, 1X, O.IX) and check or calibrate instrument with a radioactive
check source (if available). Note: At a minimum, Coleman-type
lantern mantles may be used as a check source. Lantern mantles are
treated with a substance containing radioactive Thorium oxide.
5, Turn audio switch on if desired.
6. Choose needle response (fast/slow response).
7, Turn range selector to most sensitive setting and determine natural
background radiation (0.01-0.02 mR/hr).
8, Scan suspected surfaces or areas. When in doubt, use most sensitive
ranges first. Read scale in mR/hr or counts/minutes.
Sources
Department of Health and Human Services, Bureau of Radiological Health,
Radiological Health Handbook. USGPO (017-011-004309).
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U.S. Environmental Protection Agency. "Hazardous Materials Incident
Response Operations Training Manual." National Training and Operationa
Technology Center, Cincinnati, Ohio.
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SECTION 6.0
BIBLIOGRAPHY
American Public Health Association. Standard Methods for the Examination of
Water and Wastewater, Fifteenth Edition. Washington, D.C., 1980.
American Society for Testing and Materials. Penetration Test and Split-
Barrel Sampling of Soi Is. In: Annual Book of ASTM Standards - Part 19.
D1586-67. Philadelphia, PA, 1981.
American Society for Testing and Materials. Recommended Practices for
Sampling. In: Annual Book of ASTM Standards - Part 26. D1605-60.
Philadelphia, PA, 1981.
American Society for Testing and Materials. Soil Investigation and
Sampling by Auger Borings. In: Annual Book of ASTM Standards, Part 19.
D1452-80. Philadelphia, PA, 1981.
American Society for Testing and Materials. Standard Practice
for Sampling Atmospheres to Collect Organic Compounds. (Activated
Charcoal Adsorption Method.) In: Annual Book of ASTM Standard - Part 26.
D3686-78. Philadelphia, PA, 1981.
American Society for Testing and Materials. Standard Properties for Sampling
Water. In: Annual Book of ASTM Standards - Part 31. D3370-76.
Philadelphia, PA, 1981.
American Society for Testing and Materials. Thin Walled Tube Sampling of
Soils. In: Annual Book of ASTM Standards Part 19. D-1587-74.
Philadelphia, PA, 1981.
Apperson, C. S., R. B. Leidy, R. Epler and E. Corter. An Efficient Device for
Collecting Soil Samples for Pesticide Residue Analysis. Bull. Environ.
Contain. Toxicol., 25:55-58, 1980.
Arthur D. Little, Inc. 1979. EPA/IERL-RTP Procedures for Level 2 Sampling and
Analysis of Organic Materials. EPA-600/7-79-033, U.S. Dept. of Commerce,
1979.
Barborick, K. A., B. R. Sabey and A. Klute. Comparison of Various Methods of
Sampling Soil Water for Determining Ionic Salts, Sodium and Calcium
Content in Soil Columns. Amer. Journal of Soil Science, 43(5). 1979.
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Batley, G. E., D. Gardner. Sampling and Storage of Natural Waters for Trace
Metals Analysis. Research, 11:745-756, 1977.
Beach, M. and J. S. Beach. Sample Acquisition - The First Step in Water
Qual ity Monitoring. Prog. Water Tech., 9(516):75-77, 1977.
Eichenberger, B., J. R. Edwards, K. Y. Clen and R. Stevens. A Case Study of
Hazardous Wastes in Class 1 Landfills. EPA 600/2-78-064. U.S.
Environmental Protection Agency, Washington, D.C., 1978.
Enverex, Inc. Handbook for Sampling and Sample Preservation of Water and
Wastewater. EPA-600/4-76-049. U.S. Dept. of Commerce, 1976.
Everett, L. G., K. D. Schmidt, R. M. Tinlin and D. R. Todd. Monitoring Ground
Water Quality: Methods and Costs. EPA-600/4-76-023, U.S. Environmental
Protection Agency, Washington, D.C., 1976.
Hens ley, C. P., W. J. Keffer, C. McKenzie and M. D. Lair. Continuous
Monitoring Automated Analysis, and Sampling Procedures. Journal WPCE, pp.
1061-1065, 1978.
Hurst, G. S. and J. E. Turner. Elementary Radiation Physics. John Wiley and
Sons, New York, 1967.
Johnson, M. G. The Stratified Sample Thief-A Device for Sampling Unknown
Fluids. In: National Conference on Management of Hazardous Waste Sites,
Washington, D.C., 1981.
Josephson, J. Safeguards for Groundwaters. Environmental Science and
Technology, 14(1):38-44, 1980.
Lentzen, D. E., D. Wagoner, E. D. Estes, and W. F. Gutknecht. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment (second ed.).,
EPA-600/7-78-201, 1978.
MacLeod, K. E. and R. G. Lewis., Measurement of Contamination from PCB Sources
n: Sampling and Analysis of Toxic Organics in the Atmosphere, ASTM STP
721, Philadelphia, PA, 1980.
MacLeod, K. E. Polychlorinated Biphenyls in Indoor Air. Environmental Science
and Technology, 7(11), 1981 .
Maddalone, R. F. Technical Manual for Inorganic Sampling and Analysis.
EPA-600/277-024, 1977.
Mason, Benjamin, J. Protocol for Soil Sampling: Techniques and Strategies.
EPA-600/54-83-002, U.S. Environmental Protection
Agency, 1983.
Milletari, A. F. Sampling Industrial Wastewater to Help Meet Discharge
Standards. Water and Wastes Engineering, 14(10):55-57, 1977.
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Monsanto Corp. Technical Manual for Process Sampling Strategies for Organic
Materials. EPA-2-76-122, IERL, 1976.
Peters, J. A., K. M. Tackett, and E. C. Eimutis. Measurement of Fugitive
Hydrocarbon Emissions from a Chemical Waste Disposal Site. In:
National Conference on Management of Uncontrolled Hazardous Waste Sites,
Washington, D.C., 1981.
Pellezzari, E. D. Development of Method for Carcinogenic Vapor Analysis in
Ambient Atmospheres. EPA 650/2-74-121, 1974.
Pettyjohn, W. A., W. J. Dun I op, R. Crosby, and W. J. Keely. Sampling
Groundwater for Organic Contaminants. Groundwater. 19(2), 1981.
Pickens, J. F., J. A. Cherry, G. E. Grisak, W. R. Merrit and B. A. Risto. A
Multilevel Device for Groundwater Sampling and Piezometric Monitoring.
Groundwater, 15(5), 1977.
Rhodes, J. W. and D. E. Johnson. Evaluation of Collection Media for Low
Levels of Airborne Pesticides. EPA 600/1-77-050, 1980.
Robertson, J. Organic Compounds Entering Ground Water from a Landfill.
National Environmental Research Center. PB-237-969, 1974.
Schofield, T. Sampling Water and Wastewater. Practical Aspects of Sample
Collection. Water Pollution Control, 79:468-470, 1980.
Sullivan, D. A. and J. B. Strauss. Air Monitoring of a Hazardous Waste Site.
In: National Conference on Management of Uncontrolled Hazardous Waste
Sites, Washington, D.C., 1981.
Williams, R. B. A Sample Substrate Core Sampler. Lab. Pratt., 29(6):637,
1980.
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APPENDIX A
SAMPLE CONTAINER IZATM
AND PRESERVATION
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Acidity and Alkal initv
Apparatus and Materials:
Polyethylene or borosilicate glass (Pyrex or equivalent) bottles.
Sample Collection, Preservation, and Handling:
Fill sample bottles completely and cap tightly.
Store samples at 4°C.
All samples should be analyzed within 14 days of collection.
Qua I ity Control:
Dissolved gases contributing to acidity or alkalinity, such as
carbon dioxide, hydrogen sulfide, or ammonia, may be lost or gained
during sampling or storage. Sample bottles must be capped and
sealed tightly, avoiding sample agitation or prolonged exposure to
air.
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Asbestos
Apparatus and Materials:
1-liter Polyethylene bottles
Sample Collection, Preservation and Handling:
Leave air space at the top of the sample container to allow for
shaking the sample.
Avoid contacting the sample with acid
If the sample cannot be filtered within 48 hours of collection, add
1 ml of a 2.71 percent solution of mercuric chloride per liter of
sample to prevent bacterial growth.
Store at 4°C
Qua I ity Control:
The sample bottle should be rinsed at least twice with the water
that is being sampled.
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Bacteria
Apparatus and Materials:
Polypropylene or glass bottles. Samples for bacteriological
examination must be collected in bottles that have been cleansed and
rinsed with great care, given a final rinse with distilled water,
and steri I ized.
Bottles of glass capable of being sterilized and of any suitable
size and shape may be used for samples intended for bacteriologic
examination. Bottles shall hold a sufficient volume of sample for
all the required tests, permit proper washing, and maintain the
samples uncontaminated until the examinations are completed. Ground
glass stoppered bottles, preferably wide-mouth and of
break-resistant glass, are recommended. Polypropylene bottles of
suitable size, wide-mouth, and capable of being sterilized are also
satisfactory.
Metal or plastic screw cap closures may be used on sample bottles
provided that no volatile compounds are produced on sterilization,
and that they are equipped with liners that do not produce toxic or
bacteriostatic compounds on sterilization.
Before sterilization, cover the tops and necks of sample bottles
having glass closures with metal foil, rubberized cloth, heavy
impermeable paper, or milk bottle cover caps.
Glassware shall be sterilized for not less than 60 minutes at a
temperature of 170°C.
For plastic bottles that distort on autoclaving, low temperature
ethylene oxide gas sterilization should be used.
Sodium thiosulfate (ACS), 10 percent solution. When sampling water
containing residual chlorine, sodium thiosulfate should be added to
the clean sample bottle before sterilization in an amount sufficient
to provide an approximate concentration of 100 mg/l in the sample.
This can be accomplished by adding to a 500 ml bottle, 0.4 ml of a
10 percent solution of sodium thiosulfate (this will neutralize a
sample containing about 15 mg/l of residual chlorine). The bottle
is then stoppered, capped, and sterilized.
Water samples high in copper or zinc and wastewater samples high in
heavy metals should be collected in sample bottles containing a
chelating agent that will reduce metal toxicity. This is
particularly significant when such samples are in transit for 24
hours or more. Ethyl enediaminetetraacetic acid (EDTA) is a
satisfactory chelating agent. A concentration of 372 mg/l should be
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added separately to the sample bottle before sterilization (0.3 ml
of a 15 percent solution in a 500 ml bottle) or it may be combined
with the sodium thiosulfate solution before addition.
Sample Collection, Preservation, and Handling:
When the sample is collected, leave ample air space in the bottle
(at least 2.5 cm or 1 in.) to facilitate mixing, of the sample by
shaking, preparatory to examination. Care must be exercised to take
samples that will be representative of the water being tested and to
avoid contamination of the sample at the time of collection or in
the period before examination.
The sampling bottle shall be kept unopened until the moment it is to
be filled. Remove the stopper and hood or cap as a unit, taking
care to avoid soiling. During sampling, do not handle the stopper
or cap and neck of the bottle and protect them from contamination.
Hold the bottle near the base, fill it without rinsing, replace the
stopper or cap immediately, and secure the hood around the neck of
the bottle.
Store samples at 4°C.
All samples should be analyzed within 6 hours of collection.
Qua I ity Control:
The bacteriological examination of a water sample should be started
promptly after collection to avoid unpredictable changes. The time
and temperature of storage of all samples should be recorded and
should be considered in the interpretation of data.
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B i carbonate/Carbonate
Apparatus and Materials:
Polyethylene or glass bottles
Sample Collection, Preservation and Handling:
Bicarbonate/Carbonate analysis should be performed onsite. If
onsite determination is not possible, completely fill the sample
bottle, leaving no headspace, and return it to the laboratory as
quickly as possible for analysis.
Store sample at 4°C until analyzed.
Qua I ity Control:
Carbon dioxide may be lost or gained during sampling and storage.
Sample bottles must be capped and sealed tightly, avoiding sample
agitation or prolonged exposure to air.
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Biochemical-Oxvaen Demand (BOD)
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
If possible, avoid samples containing residual chlorine by sampling
before chI orination. Notify laboratory if sample is from a
chlorinated effluent.
Store sample at 4° until analyzed.
All samples should be analyzed within 48 hours of collection.
Qua I ity Control:
Samples for BOD analysis may undergo significant degradation during
storage between collection and analysis, resulting in a low BOD
value. Minimize reduction of BOD by promptly analyzing the sample.
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Bromide
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
There are no required preservation techniques, although storage at
4°C is recommended.
All samples must be analyzed within 28 days of collection.
Qua I ity Control:
No special precautions.
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Carbonate
See Bicarbonate/Carbonate
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Chloride
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
No preservative necessary.
All samples must be analyzed within 28 days of collection,
Qua I ity Control:
No special precautions.
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Chlorine Demand
Apparatus and Materials:
Polyethylene or glass bottles.
Testing apparatus and reagents, if analysis is to be performed
onsite.
Sample Collection, Preservation, and Handling:
Chlorine in aqueous solution is unstable, and the chlorine content
of samples or solutions, particularly weak solutions, will decrease
rapidly. Exposure to sunlight or other strong light or agitation
will accelerate the reduction of chlorine. Therefore, sample must
be analyzed onsite or brought immediately to the laboratory. The
maximum holding time is 2 hours.
Qua I ity Control :
Chlorine determinations must begin immediately after sampling.
Excessive light and agitation should be avoided.
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Chromium VI
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
All samples must be analyzed within 24 hours of collection.
Do not contact sample with acid
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Chemical Oxvaen Demand (COD')
Apparatus and Materials:
Polyethylene or glass bottles.
Cone, sulfuric acid, H2S04 (ACS) .
Sample Collection, Preservation, and Handling:
Preserve the sample by acidification with cone, sulfuric acid to a
pH less than 2.
Store samples at 4°C.
All samples must be analyzed within 28 days of collection.
Qua I ity Control:
Unstable samples should be tested without delay.
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Color
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
All samples must be analyzed within 48 hours of collection.
Qua I ity Control:
No special precautions.
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Conductance
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
All samples must be analyzed within 28 days.
Qua I ity Control:
No special precautions.
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Cyanide, Total and Amenable to ChI orination
Apparatus and Materials:
Polyethylene or glass bottles.
Sodium hydroxide solution (ACS).
Ascorbic acid.
Sample Collection, Preservation, and Handling:
Because most cyanides are highly reactive and unstable, analyze
samples as soon as possible. preserve the sample by addition of
2 ml of 10 N NaOH to raise the pH of the sample to 12 or above and
store in a closed, dark bottle at 4°C.
If residual chlorine is present in the sample, add 0.6 g ascorbic
acid.
All samples should be analyzed within 14 days of collection.
Qua I ity Control:
Maximum holding time is 24 hours when sulfide is present.
Optionally, all samples may be tested with lead acetate paper before
the pH adjustment in order to determine if sulfide is present. If
sulfide is present, it can be removed by the addition of cadmium
nitrate powder until a negative spot test is obtained. The sample
is filtered and then NaOH is added to pH 12.
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Appendix A
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Fluoride
Apparatus and Materials:
Polyethylene bottles.
Sample Collection, Preservation, and Handling:
Polyethylene bottles are required for collecting and storing samples
for fluoride analysis. Always rinse the bottle with a portion of
the sample.
All samples must be analyzed within 28 days of collection.
Qua I ity Control:
No special precautions.
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Appendix A
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Hardness
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Acidify with HN03 to pH 2, store samples at 4°C.
Samples should be analyzed within 6 months of collection.
Qua I ity Control:
Serious errors may be introduced during sampling and storage by
failure to remove residues of previous samples from the sample
container; therefore all containers and sampling equipment should be
thoroughly cleaned before use.
A-18
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Hvdrazine
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Storage:
If the sample cannot be analyzed immediately, collect it under
acid. Add 90 ml of sample to 100 ml of (1 + 9) HCI: one volume
cone. HCI mixed with nine volumes H20.
Qua I ity Control:
Avoid contacting the sample with oxidizing agents which may diminish
the hydrazine content.
A-19
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Iodide
Apparatus and Materials:
Polyethylene or glass containers.
Sample Collection, Preservation, and Handling:
Store samples at 4°C, analyze within 24 hours of collection.
Qua I ity Control:
No special precautions.
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Iodine
Apparatus and Materials:
Polyethylene or glass containers
Sample Collection, Preservation, and Handling:
The samples must be analyzed onsite or brought immediately to the
laboratory. The maximum holding time is 2 hours.
Qua I ity Control:
Iodine determinations must begin immediately after sampling.
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Appendix A
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Metals - Except Chromium VI
Apparatus and Materials:
Polyethylene or glass bottles.
Nitric acid (1 + 1): Mix equal volumes of cone, nitric acid, HN03
(ACS), with deionized water.
Deionized water.
Sample Collection, Preservation, and Handling:
t Wash and rinse sample container thoroughly with 1 + 1 nitric acid,
then with deionized water before use.
Acidify the sample with 1 + 1 nitric acid to a pH of 2.0 or less.
Normally, 3 ml of 1 + 1 nitric acid per liter should be sufficient
to preserve the samples. This will keep the metals in solution and
minimize their adsorption on the container wall.
All samples should be analyzed within 6 months of collection. An
exception is mercury analysis, which must be completed within 28
days.
Qua I ity Control:
Serious errors may be introduced during sampling and storage by
failure to remove residues of previous samples from the sample
container; therefore, follow the described rinsing procedure for all
containers and sampling equipment.
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Appendix A
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N itrogen
Ammon i a
Nitrate-Nitrite
Kj el dan I Nitrogen
A-23
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Appendix A
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Page 24 of 52
Ammon i a
Apparatus and Materials:
Polyethylene or glass bottles.
cone, sulfuric acid, H2S04 (ACS).
Sample Collection, Preservation, and Handling:
In the event that a prompt analysis is impossible, add cone,
sulfuric acid to lower sample pH to less than 2.
All samples should be analyzed within 28 days of collection,
Store samples at 4°C.
Qua I ity Control:
The most reliable results are obtained from fresh samples.
A-24
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Appendix A
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KJ el dan I Nitrogen
Apparatus and Materials:
Polyethylene or glass bottles.
cone, sulfuric acid (H2S04) (ACS).
Sample Collection, Preservation, and Handling:
Acidify samples with cone, sulfuric acid to a pH of 2.0 or less.
Store samples at 4°C.
All samples should be analyzed within 28 days of collection.
Qua I ity Control:
The most reliable results are obtained in fresh samples. If prompt
analysis is impossible, retard biological activity with the above
preservation method.
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litrate and Nitrite
Apparatus and Materials:
Polyethylene or glass bottles.
cone, sulfuric acid, I^SO^ (ACS)
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
All samples should be analyzed within 48 hours of collection.
If nitrate or nitrate plus nitrite are to be determined, preserve
the sample by addition of ^$04 to a pH of 2.0 or less.
Sulfuric acid should not be added to samples requiring analysis for
nitrite only.
Qua I ity Control :
Nitrate and nitrite determinations should be made promptly after
samp I ing.
A-26
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Appendix A
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Oi I and Grease
Apparatus and Materials:
Glass bottles.
Cone, sulfuric acid (HgStty) (ACS).
Sample Collection, Preservation, and Handling:
Collect a representative sample in a wide-mouth glass bottle and
acidify in the sample bottle with cone, sulfuric acid to a pH of 2.0
or less. If other parameters are to be analyzed for, collect a
separate sample for the oil and grease determination to avoid
subdividing the sample in the laboratory.
Store samples at 4°C.
All samples should be analyzed within 28 days of collection.
Qua I ity Control
Because losses of grease will occur on sampling equipment, the
collection of a composite sample is impractical. Individual
portions collected at prescribed intervals must be analyzed
separately to obtain the average concentration over an extended
period of time.
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Appendix A
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Organics
Purgeables - Method 624
ExtractabIes - Method 625
Pesticides/PCBs - Method 608
A-28
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Appendix A
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Method 624 Puraeables
Apparatus and Materials:
a The water sample is to be collected in two (2) 40 ml vials with
Teflon-faced silicone septa and screw caps and maintained at 4°C
until the sampler's responsibility has been relieved at the Sample
Bank.
Container Preparation
1. Wash 40 ml vials with screw caps (Pierce No. 13075 or
equivalent) and Teflon-faced silicone septa (Pierce No. 12722
or equivalent) separately, utilizing a solution of Alconox
detergent or equivalent, and hot tap water.
2, Rinse thoroughly with de ionized water.
3, Place vials, caps, and septa on prec leaned aluminum foil (as
described above) and bake in an oven for one hour at 105°C.
Allow the vials to cool with the septa properly inserted
the caps screwed on loosely. Tighten down caps when cool
and
5, Store vials in an area not subject to contamination by air or
other sources.
Sample Collection, Preservation, and Handling
t If the sample contains residual chlorine, add sodium thiosulfate as
a preservative (10 mg/40 ml is sufficient for up to 5 ppm Cl2) to
the empty sample bottles just prior to shipping to the sampling site.
If aromatic compounds such as benzene, toluene and ethyl benzene are
to be determined one of the following procedures should be used to
minimize degradation of these compounds by microbial action.
Collect about 500 ml of sample in a clean container. Adjust
the pH of the sample to about 2 by addition of 1+1 HCI. Cap
the container and invert once to mix; check the pH with narrow
range (1.4 to 2.8) pH paper. Transfer the sample to a 40 ml
vial as described below. If residual chlorine is present, add
sodium thiosulfate to another sample container and fill as
described below.
Alternatively, the addition of the HgCl2 to the samp I ing vial
(approximately 12 mg per 40 ml vial) has been found effective
for inhibiting microbial action.
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Appendix A
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The following procedures apply to sampling directly with the sample
vial .
1. Collect a single undisturbed sample of water for the analysis
of volatile organics. Submerge the sample vial just below the
surface upside down and slowly invert. Accomplish this task
creating as little disturbance as possible.
2, Allow the vial to fill and reach equilibrium with its
surrounding reservoir for several seconds.
3, Place the cap over the mouth of the vial so that the septum is
properly oriented and screw down the cap firmly.
4, Invert the vial to discover any entrapped air bubbles. If such
is the case, the sample will be discarded and another 40 ml vial
selected and fi I led.
5, Collect a replicate sample per instructions above.
Label the sample vials with the appropriate designated
sample tag.
Place the properly labeled sample vials in an appropriate
carrying container maintained at 4°C throughout the
sampling and transportation period.
Analyze samples within 14 days.
Qua I ity Control
Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the
precision of the sampling techniques.
Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride) through the septum seal into the
sample during shipment and storage. A field blank* prepared from
organic-free water and carried through the sampling and handling
protocol can serve as a check on such contamination.
*Field Blank. The field blank is defined as an appropriate volume of
"organic-free" water which has been sent to the sampling site and back to
the analytical laboratory in a container and bottle identical to the type
used to collect the samples. Field blanks and samples must be shipped in
separate containers. When received in the lab, the field blank is analyzed,
as if it were an actual sample.
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Appendix A
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Method 625 Extractables fBase/Neutrals, Acids and Pesticides!
Apparatus and Materials:
Sampling equipment, for discrete or composite sampling.
Grab sample bottle - Amber glass, 1 liter to 1 gallon volume.
French or Boston Round design is recommended. The container must be
washed and solvent rinsed before use to minimize interferences.
Bottle caps - Threaded to fit sample bottles. Caps must be lined
with Teflon. Aluminum foil may be substituted if sample is not
corrosive.
Compositing equipment - Automatic or manual compositing system.
Must incorporate glass sample containers for the collection of a
minimum of 1000 ml. Sample containers must be kept refrigerated
during sampling. No plastic or rubber tubing other than Teflon may
be used in the system.
Sample Collection, Preservation, and Handling:
t Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must
not be prerinsed with sample before collection. Composite samples
should be collected in refrigerated glass containers. Automatic
sampling equipment must be free of Tygon and other potential sources
of contamination.
t The sample must be iced or refrigerated from the time of collection
unti I extraction.
All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
Qua I ity Control:
Standard quality assurance practices should be used with this
method.
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Appendix A
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Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This
should be followed by detergent washing in hot water. Rinse with
tap water, distilled water, acetone and finally pesticide quality
hexane. Heavily contaminated glassware may require treatment in a
muffle furnace at 400°C for 15 to 30 minutes. Some high boiling
materials, such as PCB's, may not be eliminated by this treatment.
Glassware should be sealed/stored in a clean environment immediately
after drying or cooling to prevent any accumulation of dust or other
contaminants. Store inverted or capped with aluminum foil.
A-32
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Appendix A
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Method 608 Oraanochlorine Pesticides and PCBs
Apparatus and Materials:
Sampling equipment, for discrete or composite sampling.
Grab sample bottle - Amber glass, 1 liter or 1 quart volume. French
or Boston Round design is recommended. The container must be washed
and solvent rinsed before use to minimize interferences.
Bottle caps - Threaded to screw on to the sample bottles. Caps must
be lined with Teflon. Foil may be substituted if sample is not
corrosive.
Compositing equipment - Automatic or manual compositing system.
Must incorporate glass sample containers for the collection of a
minimum of 25U ml. Sample containers must be kept refrigerated
during sampling. No Tygon or rubber tubing may be used in the
system.
Sample Collection, Preservation, and Handling:
Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must
not be prewashed with sample before collection. Composite samples
should be collected in refrigerated glass containers. Automatic
sampling equipment must be free of Tygon and other potential sources
of contamination.
t The samples must be iced or refrigerated from the time of collection
unti I extraction.
All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
Qua I ity Control:
Standard quality assurance practices should be used with this method.
A-33
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Appendix A
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Hydrogen Ion (pH)
Apparatus and Materials:
Polyethylene or glass bottles.
Electronic pH meter with temperature compensation adjustment. Glass
electrode: Glass electrodes are available for measurement over the
entire pH range. Use minimum-sodium-ion-error type electrodes for
high-pH high-sodium samples. Reference electrode: Use calomel,
silver-silver chloride, or other constant-potential electrode.
Standard buffer solutions of known pH.
Sample Collection, Preservation, and Handling:
The eIectrometric measurement of pH is the only method approved by
EPA. The determination should be made onsite. The maximum holding
time for any sample is 2 hours.
Because of the difference between the many makes and models of
commercially available pH meters, it is impossible to provide
detailed instructions for the proper operation of every instrument.
In each case, follow the manufacturer's instructions. Thoroughly
wet the glass and reference electrodes by immersing the tips in
water overnight or in accordance with instructions. Thereafter,
when the meter is not in use for pH measurement, keep the tips of
the electrodes immersed in water.
Before use, remove the electrodes from the water and rinse with
distilled or demineral ized water. Dry the electrodes by gently
blotting with a soft tissue. Standardize the instrument with the
electrodes immersed in a buffer solution with a pH approaching that
of the sample and note the temperature of the buffer and the pH at
the measured temperature. Remove the electrodes from the buffer,
rinse thoroughly, and blot dry. Immerse in a second buffer
approximately 3 pH units different from the first and note the
temperature of the buffer and the pH at the measured temperature;
the reading should be within 0.1 unit of the pH for the second
buffer. Rinse electrodes thoroughly, blot dry, and immerse in the
sample. Agitate the sample sufficiently to provide homogeneity and
keep solids in suspension. If the sample temperature is different
from that of the buffers, let the electrodes equilibrate with the
sample. Measure the sample temperature and set the temperature
compensator on the pH meter to the measured temperature. Note and
record the pH and temperature. Rinse electrodes and immerse in
water unti I the next measurement.
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Appendix A
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When only occasional pH measurements are made, standardize the
instrument before each measurement. Where frequent measurements are
made, less frequent standardization (every 1 or 2 hours) is
satisfactory. However, if sample pH values vary widely, standardize
more frequently with a buffer having a pH within 1 to 2 pH units of
that sample. Measure with two or more buffers of different pH at
least once daily and more frequently if samples contain abrasive
solids or dissolved fluorides, in order to check the linearity of
response. When electrode response to two buffers 3 pH units apart
show differences greater than 0.1 pH unit, replace the glass
electrode.
Measurements of pH in high purity waters, such as condensate or
demineraI izer effluents, are subject to atmospheric contamination
and require special procedures for accurate pH measurement.
Qua I ity Control
The glass electrode is relatively free from interference from color,
turbidity, colloidal matter, oxidants, reductants, or high salinity,
except for a sodium error at high pH. This error at a pH above 10
may be reduced by using "low sodium error" electrodes. When using
ordinary glass electrodes, make approximate corrections for the
sodium error in accordance with information supplied by the
manufacturer. Temperature exerts two significant effects on pH
measurement. The pH potential, i.e., the change in potential per pH
unit, varies with temperature, and ionization in the sample also
varies. The first effect can be overcome by a temperature
compensation adjustment provided on the better commercial
instruments. The second effect is inherent in the sample and is
taken into consideration by recording both the temperature and pH of
each sample.
A-35
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Appendix A
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Page 36 of 52
Phenols
Apparatus and Materials:
G I ass bott I es .
0 Concentrated Sulfuric Acid, fySfy (ACS).
Sample Collection, Preservation, and Handling:
t Acidify sample with concentrated 1^504 acid to a pH of 2.0 or
less.
t Oxidizing agents, such as chlorine, should be removed immediately
after sampling by the addition of an excess of ferrous ammonium
su I fate .
t Store samples at 4°C.
All samples should be analyzed within 28 days of collection.
Qua I ity Control :
Phenols in concentrations usually encountered in wastewaters are
subject to biological and chemical oxidation. It is recommended
that preserved and stored samples be analyzed as soon as possible.
A-36
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Appendix A
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Orthophosphate
Apparatus and Materials:
t Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
All samples must be analyzed within 48 hours of collection.
Qua I ity Control:
t Do not store samples containing low concentrations of phosphorus in
plastic bottles because phosphate may be adsorbed onto the walls of
the bottles. Rinse all glass containers with hot dilute HCI, then
rinse several times in distilled water. Never use commercial
detergents containing phosphate for cleansing glassware used in
phosphate analyses.
A-37
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Appendix A
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Phosphorus, Total
Apparatus and Materials:
Polyethylene or glass bottles.
cone, sulfuric acid (HgSO,^) (ACS).
Sample Collection, Preservation, and Handling:
Acidify sample with cone, sulfuric acid to a pH of 2.0 or less.
t Store samples at 4°C.
All samples must be analyzed within 28 days of collection.
Qua I ity Control :
t Do not store samples containing low concentrations of phosphorus in
plastic bottles because phosphate may be adsorbed onto the walls of
the bottles. Rinse all glass containers with hot dilute HCI, then
rinse several times in distilled water. Never use commercial
detergents containing phosphate for cleansing glassware used in
phosphate analyses.
A-38
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Appendix A
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Rad i oact i v i ty
Apparatus and Materials:
Polyethylene or glass bottles.
t Cone, nitric acid (HNOs) (ACS).
Sample Collection, Preservation, and Handling:
Acidify samples with cone, nitric acid to a pH of 2.0 or less.
All samples must be analyzed within 6 months of collection.
Qua I ity Control :
The principles of representative sampling of water and wastewater
apply to sampling for radioactivity examinations. When radioactive
industrial wastes or comparable materials are sampled, consideration
should be given to the deposition of radioactivity on the walls and
surfaces of glassware, plastic containers, and equipment. Because a
radioactive element is often present in submicrogram quantities, a
significant fraction of it may be readily lost by adsorption on the
surface of containers or glassware used in the examination. This may
cause a loss of radioactivity and possible contamination of subsequent
samples due to reuse of inadequately cleansed containers.
A-39
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Appendix A
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Apparatus and Materials:
Polyethylene bottles.
Sample Collection, Preservation, and Handling:
t Collect samples in bottles of polyethylene plastic only; do not use
glassware for any sample handling.
Store samples at 4°C.
All samples must be analyzed within 28 days of collection.
Qua I ity Control:
t If samples are stored in glass, silica may leach into the sample and
raise concentrations, therefore glassware cannot be used.
A-40
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Appendix A
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Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
Samples must be analyzed within the following times, according to the
analysis to be performed:
Dissolved
VoI at i Ie D i ssoIved
Suspended
Volati le Suspended
Total
VoI at i Ie TotaI
Sett IeabIe
7 days
7 days
7 days
7 days
7 days
7 days
48 hours
Qua I ity Control
Sample should be analyzed as soon as possible after collection for
best results.
Exclude unrepresentative particles such as leaves, sticks, or large
sol ids.
Glass bottles are desirable. Plastic bottles are satisfactory
provided that the material in suspension in the sample does not
adhere to the walls of the container. Store samples that are likely
to contain iron or manganese so that oxygen will not come into
contact with the water. Analyze these samples promptly to minimize
the possibility of chemical or physical change during storage.
A-41
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Appendix A
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Page 42 of 52
SuI fate
Apparatus and Materials:
t Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
In the presence of organic matter, certain bacteria may reduce
sulfate to sulfide. To avoid this, samples are stored at 4°C.
t All samples must he analyzed within 28 days of collection.
Qua I ity Control:
No special precautions.
A-42
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Appendix A
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Sulfide
Apparatus and Materials:
Polyethylene or glass bottles.
Zinc Acetate rZn(C2H30?)2], 2 N.
Sodium hydroxide (NaOH), 6 N.
Sample Collection, Preservation, and Handling:
t Take sample with a minimum of aeration. Preserve sample by addition
of 2 ml of 2N zinc acetate; raise pH to 9 using NaOH. Fill sample
bottle completely allowing no headspace.
Store sample at 4°C.
All samples must be analyzed within 7 days of collection.
Dual ity Control:
It is important that all sample bottles are sealed airtight, with no
entrapped air.
A-43
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Appendix A
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Page 44 of 52
Sulfite
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Collect a fresh water sample, allow as little contact with air as
possible, as air will oxidize the sulfite to sulfate.
t All samples should be analyzed onsite.
Qua I ity Control:
It is important that all sample bottles be sealed airtight, with no
entrapped air.
A-44
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Appendix A
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Page 45 of 52
Surfactants
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
t Store samples at 4°C.
t All samples must be analyzed within 48 hours of collection,
Qua I ity Control:
No special precautions.
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Appendix A
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Total Organic Carbon fTPC)
Apparatus and Materials:
t Glass bottles, with Teflon lined caps.
cone, hydrochloric acid (H2S04) (ACS).
Sample Collection, Preservation, and Handling:
t Acidify samples with cone, hydrochloric acid to a pH of 2.0 or less.
Store samples at 4°C.
t All samples should be analyzed within 28 days of collection.
Qua I ity Control:
Avoid exposure of the sample to light and atmosphere, minimize
storage time.
A-46
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Appendix A
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Page 47 of 52
Total Organic Hal ide CTOX)
Apparatus and Materials:
Glass bottles, amber, with Teflon lined caps.
t Sodium sulfite, Na;>S03, 0.1 M
Sample Collection, Preservation, and Handling:
t If amber glass bottles are not available, samples should be protected
from I ight.
Samples should be stored at 4°C without headspace.
Reduce residual chlorine by the addition of 1 ml of 0.1 M sodium
sulfite per liter of sample.
TOX may increase with storage, therefore, samples should be analyzed
as soon as possible after collection; maximum holding time should
not exceed 7 days.
Qua I ity Control:
Glassware used in TOX sampling and analysis must be thoroughly
cleaned. All glassware should be washed using detergent and hot
water, rinsed with tap water and, as a final rinse, deionized
water. Drain dry and heat at 105°C for 1 hour. Glassware should be
sealed and stored in a clean area after drying and cooling.
A-47
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Appendix A
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Page 48 of 52
Turbidity
Apparatus and Materials:
Polyethylene or glass bottles.
Sample Collection, Preservation, and Handling:
Store samples at 4°C.
t All samples must be analyzed within 48 hours of collection.
Qua I ity Control:
Turbidity analysis should be performed on the day the sample is
taken. If longer storage is unavoidable, store samples in the dark
for up to 48 hours. Prolonged storage before measurement is not
recommended because irreversible changes in turbidity may occur.
A-48
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TABLE A-l. RECOMMENDED SAMPLING AND PRESERVATION PROCEDURES FOR WATER AND WASTEWATER
Parameter
Acidity
Alkalinity
Asbestos
Bacteria
Bicarbonate
BOD
Bromide
Carbonate
> Chloride
1
Jo Chlorine
demand
Chromium VI
COD
Color
Conductance
Cyanide
Fluoride
Hardness
Hydrazlne
Collection
technique
Grab or composite
Grab or composite
Grab or composite
Grab only
Grab only
Grab only
Grab or composite
Grab only
Grab or composite
Grab only
Grab or composite
Grab only
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Container8
P.G
P.G
P
Pro, G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P.G
P
P.G
P.G
Preservation Holding time0
Cool, 4'C
Cool, 4'C
Cool, 4'C
Cool, 4'C, 10*
N32S203, EDTA
Determine onslte
Cool, 4'C
None required
Determine onslte
None required
Determine onslte
Cool. 4'C
HzSO* to pH <2;
Cool, 4'C
Cool, 4'C
Cool, 4'C
NaOH to pH >12, 0.6g
Ascorbic acldd
None required
HN03 to pH <2
If not analyzed
Immediately, collect
under acid. Add 90 ml
of sample to 10 ml
(1 + 9) HC1
14 days
14 days
48 hours
6 hours
No holding
48 hours
28 days
No holding
28 days
No holding
24 hours
28 days
48 hours
28 days
14 days
28 days
6 months
7 days
Minimum
required
volume
(H)
100
100
1000
200
100
1000
100
100
50
200
100
50
50
100
500
300
100
100
t
"d TO >
CD 05 ~O
CO < T3
05 05
ZJ
J^ Q.
coo --
0
-b o >
en
hO
(continued)
-------
TABLE A-l (continued)
en
O
Parameter
Iodide
Iodine
Metals (Except Cr
Dissolved
Suspended
Total
Nitrogen
Ammonia
Kjeldahl
(total)
Nitrate plus
Nitrite
Nitrate
Nitrite
Oil and Grease
Organlcs
Extractables
base/neutrals
and acids)
Collection
technique
Grab or composite
Grab only
VI)
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab only
Grab or composite
Container*
P.6
P.G
P.G
P.G
P,G
P.G
P.G
P,G
P.G
P.G
G
G, Teflon-
lined cap
Preservation
Cool 4'C
Determine onslte
Filter onslte. HW>3
to pH <2
Filter onslte
HN03 to pH <2
Cool, 4'C, H2S04
to pH <2
Cool. 4*C, H2S04
to pH <2
Cool, 4*C. H2S04
to pH <2
Cool, 4'/C. H2S04
to pH <2
Cool 4*C, H2S04
to pH <2
Cool 4*C. H2S04
to pH <2
Cool, 4*C
Minimum
required
volume
Holding time* (ml)
24 hours 100
No holding 500
months, except 200
Hg 28 days
6 months, except 200
Hg 28 days
6 months, except 100
Hg 28 days
28 days 400
28 days 500
28 days 100
48 hours 100
48 hours 50
28 days 1000
7 days until 1000
extraction, 30
days after
extraction
i
"d TO >
Q) CD ~O
CD CD
cn O-
00
Z! X
O
-b o >
cn
(continued)
-------
TABLE A-l (continued)
Parameter
Organlcs (cent.)
Purgeables
(halocarbons-
aromatlcs)
Purgeables
(acroleln and
acrylonltrlle)
Pesticides and
PCBs
PH
?" Phenol
en
Phosphorus
Ortho
phosphate
Phosphorus,
Total
Radioactivity
Silica
Dissolved
Total
Solids
Dissolved
Volatile
Dissolved
Suspended
Collection
technique
Grab only
Grab only
Grab or composite
Grab only
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Contal ner*
6, Teflon-
lined cap
G. Teflon-
lined cap
G, Teflon-
lined cap
P.G
G
P,6
P.G
P.G
P
P
P,G
P.G
P.G
Preservation
Cool, 4'C
Cool, 4'C
Cool, 4'C
Determine onslte
Cool. 4'C. H2S04
to pH <2
Filter onslte,
cool, 4'C
Cool, 4'C. H2S04
to pH <2
HNOa to pH <2
Cool, 4'C
Cool, 4'C
Cool, 4'C
Cool, 4'C
Cool, 4'C
Holding tlmeb
14 days
14 days
7 days until
extraction, 30
days after
extraction
2 hours
24 hours
48 hours
28 days
6 months
28 days
28 days
7 days
7 days
7 days
Minimum
required
volume
(H)
40
40
250
25
500
50
50
1 gal
50
50
100
100
100
"d TO >
Q> 05 ~O
CO < ~O
05 05
(/> 3
cn Q.
_> o
Z! X
0
-b o >
cn
ho
-------
TABLE A-l (continued)
en
ho
Parameter
Solids (cont.)
Volatile
Suspended
Total
Volatile Total
Settleable
Sulfate
Sulflde
Sulflte
Surfactants
TOC
TOX
Turblty
*P Polyethylene
Collection
technique
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
Grab or composite
, G » Glass, Pro
bThe holding times are those listed
Hastes. EPA-600/4-82-055 and Methoi
Container* Preservation Holding tlmeb
P,G
P,G
P.G
P,6
P.6
P.G
P.G
P.G
G, Teflon-
lined cap
G, Amber,
Teflon-lined
cap
P.G
Polypropylene
In Technical Additions
Is for Organic Chemical
Cool» 4'C
Cool, 4*C
Cool, 4*C
Cool, 4*C
Cool, 4*C
Cool, 4*C, 2 ml zinc
acetate plus NaOH to
pH >9
Determine onslte
Cool, 4*C
Cool, 4*C, HC1 to
pH <2
Cool, 4*C, add 1 ml
0.1 N sodium sulflte
Cool, 4*C
to Methods for Chemical
7 days
7 days
7 days
48 hours
28 days
7 days
No holding
48 hours
28 days
7 days
48 hours
Analysis of
Analysis of Municipal and Industrial
Minimum
required
volume
(ml)
100
100
100
100
50
500
50
250
25
100
100
Hater and
Wastewater,
cif samples cannot be filtered within 48 hours, add 1 ml of a 2.711 solution of mercuric chloride to Inhibit
bacterial growth.
dShould only be used In the presence of residual chlorine.
"d TO >
Q> 05 T3
CO < T3
05 05
(/) 3
cn Q-
hO O
Z! X
o
-h o >
cn
ho
-------
APPENDIX B
EQUIPMENT AVAILABILITY AND FABRICATI
Appendix B
Rev i s i on 0
Page 1 of 12
-------
Appendix B
Rev i s i on 0
Page 2 of 12
EQUIPMENT AVAILABILITY
Apparatus
t Stainless Steel Scoops, Trays, Beakers, Ladles
8,9,15
Thin Wall Tube Samplers, Soil Augers, Hand Corers
45,50
Gravity Corers, Dredges and Grabs
40,45
Thiefs and Triers
9,34
Water Level Indicators
38,45
Down Hole Submersible Probes
23,25,43,51
Bai lers, Col iwasa
26,34,48
t Peristaltic Pumps
8,9,15,29
Gas Displacement Pumps
5,48
Combustible Gas Detectors
3,13,16,17,33,36,41
t Oxygen Monitors
6,13,16,17,33,36,41
Portable Flame lonization Detectors
1,2
Portable Photoionization Detectors
22,37
Stain Detector Tubes
7,17,31,33,35
Personal Sampling Pumps
7,11,14,19,28,32,33,39,46
t High Volume Air Samplers
18,39,44
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Appendix B
Revision 0
Page 3 of 12
Radiation Dosimeters
4,10,20,47,49
Radiation Film Badges
12,20,24,42
Radiation Survey Instruments
4,10,12,20,21,27,30,47,49
Vendors
1. Ana labs, Inc.
80 Republ ic Drive
North Haven, CT 06473
(203) 288-8463
2, Analytical Instrument Development, Inc.
Rt. 41 and Newark Rd.
Avondale, PA 19311
(215) 268-3181
3, Bacharach Instrument Company
301 Alpha Drive
Pittsburgh, PA 15238
(412) 782-3500
4, Ba i rd Atom i c
125 Middlesex Turnpike
Bedford, MA 01730
(617) 276-6000
5, BarCad System, Inc.
P.O. Box 424
Concord, MA 01742
(617) 969-0050
6. Beckman Instruments, Inc.
Process Instrument Division
2500 Harbor Boulevard
Fullerton, CA 92634
7, Bendix Corporation
Environmental and Process Instruments Division
P.O. Drawer 831
Ronceverte, WV 24970
(304) 647-4358
8, Cole Palmer
7425 North Oak Park Ave.
Chicago, I I I inois 60648
(800) 323-4340 B-3
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Appendix B
Revision 0
Page 4 of 12
9, Curt in Matheson Scientific
Major Metropolitan Areas
10, Dosimeter Corporation of America
P.O. Box 42377
Cincinnati, OH 45242
(513) 489-8100
11. DuPont Company
Applied Technology Division
Concord Plaza - Clayton Bldg.
Wi Imington, DE 19898
(302) 772-5989
12, Eberline Instruments
P.O. Box 2108
Santa Fe, NM 87501
(505) 471-3232
13. Energetic Science
Six Sky I ine Drive
Hawthorne, NY 10532
14, Environmental Measurements, Inc.
215 Leidesdorff Street
San Francisco, CA 94111
(415) 398-7664
15, Fisher Scientific
Major Metropolitan Areas
16, Gas Measurement Instruments Ltd.
Inchinnan Estate
RenfrewPA49RG
(041) 812-3211
17, GasTech Inc.
Johnson Instrument Division
331 Fa i rch i Id Drive
Mountain View, CA 94043
(415) 967-6794
18, General Metal Works Inc.
8368 Bridgetown Road
Vi I I age of CI eves, OH 45002
(513) 941-2229
19. Gilian Instrument Corp.
1275 Route 23
Wayne, NJ 07470
(201) 696-9244 ,
D-4
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Appendix B
Revision 0
Page 5 of 12
20. Gulf Nuclear
202 Medical Center Boulevard
Webster, TX 77598
(713) 332-3581
21. Health Physics Instruments
124 San Pel icia Drive
Go I eta, CA 93117
(805) 685-2612
22. HNU Systems, Inc.
30 Oss i pee Road
Newton Upper Falls, MA 02164
(617) 964-6690
23. Hydro lab Corporation
P.O. Box 9406
Austin, TX 78766
(512) 255-8841
24. ICN Dosimetry Service
26201 Ni les Road
Cleveland, OH 44128
(216) 831-3000
25. Industrial and Environmental Analysts Inc.
P.O. Box 626
Essex Junction, VT 05452
(802) 878-5138
26. Johnson Division
UOP, Inc.
St. Paul, MN 55164
(612) 636-3900
27. Johnston Laboratories
P.O. Box 20086
383 Hi I I en Road
Towson, MD 21204
(301) 337-8700
28. Kurz Instruments Inc.
P.O. Box 849
Carmel Valley, CA 93924
(408) 659-3421
29. Leonard Mold and Die
960 West 48th Avenue
Denver, CO 80221
(303) 433-7101
B-5
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Appendix B
Revision 0
Page 6 of 12
30. Ludlum Measurements
P.O. Box 248
Sweetwater, TX 79556
(915) 235-5494
31. Matheson Safety Products
P.O. Box 85
932 Paterson Plank Road
East Rutherford, NJ 07073
(201) 933-2400
32. MDA Scientific, Inc.
1815 Elmdale Ave.
Glenview, IL 60025
33. Mine Safety Appliance Co.
600 Penn Center Boulevard
Pittsburgh, PA 15235
34. Nasco
901 Janesvi Ile Ave.
Fort Atkinson, Wl 53538
(414) 563-2446
35. National Draeger, Inc.
101 Technology Drive
Pittsburgh, PA 15275
(412) 787-8383
36. National Mine Service Company
Industrial Safety Division
355 N. Old Steubenvi Me Pike
Oakdale, PA 15071
(412) 788-4353
37. Photovac, Incorp.
134 Doncaster Ave.
Unit 2
Thornh i I I
Ontario, Canada L3T1L3
38. Powers Electric Products Company
P.O. Box 11591
Fresno, CA 93774
39. Research Appliance Company
Moose Lodge Road
Cambridge, MD 21613
(301) 228-9505
B-6
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Appendix B
Rev i s i on 0
Page 7 of 12
40. Research Instrument Manufacturing Co. Ltd,
RR No. 2 Guelph
Ontario, Canada N1H6H8
(519) 822-1547
41. Rexnord Safety Products/Biomarine Ind.
45 Great Valley Parkway
Malvern, PA 19355
(215) 647-7200
42. R.S. Landauer Jr. Company
Division of Technical Operations, Inc.
Science Road
Glenwood, IL 60425
(312) 755-7000
43. Sensorex
9713 Bolsa Ave.
Westminster, CA 92683
(714) 554-7090
44. Sierra Instruments Inc.
P.O. Box 909
Carmel VaI ley, CA 93924
(408) 659-3177
45. Soi I test, Inc
2205 Lee Street
Evanston, IL 60202
(312) 869-5500
46. Spectrex Corporation
3594 Haven Ave.
Redwood City, CA 94063
(415) 365-6567
47. Technical Associates
7051 Eton Avenue
Canoya Park, CA 91303
(213) 883-7043
48. Timco Manufacturing Company, Inc.
P.O. Box 35
Prairie Du Sac, Wl 53578
(608)-643-8534
49. Victoreen, Inc.
10101 Woodland Ave.
Cleveland, OH 44104
(216) 795-8200
B-7
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Appendix B
Rev i s i on 0
Page 8 of 12
50. Wi Idco
301 Cass Street
Saginaw, Ml 48602
(517) 799-8100
51. Yellow Springs Instrument Co.
Ye I low Springs, OH 45387
(513) 767-7241
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Appendix B
Rev i s i on 0
Page 9 of 12
EQUIPMENT FABRICATI
Many of the instruments and devices listed previously can also be readily
fabricated in-house. This usually affords considerable cost savings as well as
allows for custom designs and alterations.
Bailers, coliwasas and hand corers can be constructed from available
stainless steel and teflon stock. The diagrams and drawings which accompany
their description in the text show nominal dimensions and construction
materials. Sizes can however be altered to fit particular needs. The sources
cited with these drawings as well as the references at the end of the method
comment further on their construction and use.
The device used in Method IV-13: Sampling of Headspace Gases in Sealed
Vessels, is not currently available through commercial sources. The
fabrication details are therefore included in this Appendix.
B-9
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Appendix B
Revision 0
Page 10 of 12
Sealed Vessel Tapping Device Assembly
1. Fabricate mounting plate.
2, Position Portalign on mounting plate, drill 6.4 mm holes through Portalign
base and mounting plate. Tap holes for 7.14 mm thread in mounting plate.
Secure Portalign to mounting plate with 7.14 mm SAE bolts.
3, Thread ball valve into mounting plate.
4, Thread Swagelok cross assembly onto ball valve.
5, Insert drill bit into chuck of drill.
6. Insert drill into Portalign assembly per manufacturer's instruction. Pass
drill bit through Teflon ferrule.
7, Place part 101-6 so that it stops drill bit travel approximately 10 mm
below bottom of gasket material on mounting plate.
8. Mount entire assembly onto container using standard steel strap packaging
equ i pment.
9, Place springs over Portalign guide rods.
10, Push springs down until good tension is obtained. Secure with extra 101-6
and 101-8 parts.
11. Finger tighten compression nut containing Teflon ferrules.
B-10
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Appendix B
Revision 0
Page 11 of 12
DRILLING MEGHAN I
Parts
Mounting Plate-- 12.7 mm thick x 76 mm wide x 127
I ong, mild stee I .
2, Ball Valve--
3. Swage I ok Cross--
4. Drill Bit--
5, Dri
PortaI ign Dri
Assembly--
19.1 mm x 3.2 mm deep channel on top of each side. A
6.4 mm NPT hole in center of plate.
Bottom of mounting plate covered with 4.8
closed cell Neoprene gasket.
thick
316 stainless steel, 6.4 mm male NPT thread one end,
6.4 mm female PNT other end.
316 stainless steel, three sides 6.4 mm male NPT, 6.4
mm Swage I ok side.
AssembIe as FoI Iows:
A. 0-50 psig pressure gauge, 6.4
one side of cross.
female NPT to
B. 316 stainless steel, 6.4 mm male NPT to 6.4
Swage I ok needle valve, mount opposite pressure
gauge.
c. 6.4 mm Teflon ferrules into 6.4 mm Swage I ok
fitting.
4 mm dri I I bit, 140
12 mm long.
long, flutes approximately
Skill Model No. 2002 hand drill, cordless. Wired to
operate remotely at 300 rpm. Interlocked with
microswitch attached to depth stop.
PortaI ign, PortaI ign Tool Company, San Diego,
California, as shown below.
B-11
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Appendix B
Revision 0
Page 12 of 12
Parts List
101.1
Portal ign dri I I guide
Additional Parts Required Per Assembly
2 each 101-8
2 each 101-6
From PortaI ign
2 each Springs to fit over guide rods of PortaI ign approximately
30 kg force each spring when compressed.
B-12
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Appendix C
Revision 0
Page 1 of 23
APPENDIX C
PACKING, MARKING, LABELING, AND SHIPPING
OF HAZARDOUS MATERIAL SAMPLES
Portions of this Appendix have been taken,
by permission, from EPA/ERT
'Hazardous Materials Incident Response Operations"
Training Course Manual (165.1)
C-1
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Appendix C
Rev i s i on 0
Page 2 of 23
INTRODUCTION
Samples collected during a response to a hazardous material incident may
have to be transported elsewhere for analysis. The Environmental Protection
Agency (EPA) encourages compliance with Department of Transportation (DOT)
regulations governing the shipment of hazardous materials. These regulations
(49 CFR parts 171 through 179) describe proper marking, labeling, packaging
and shipment of hazardous materials, substances and wastes. In-particular,
part 172.402(h) of 49 CFR is intended to cover shipment of samples of unknown
materials destined for laboratory analysis.
ENVIRONMENTAL SAMPLES VERSUS HAZARDOUS MATERIAL SAMPLES
Samples collected at an incident should be classified as either
environmental or hazardous material (or waste) samples. In general,
environmental samples are collected offsite (for example from streams, ponds,
or wells) and are not expected to be grossly contaminated with high levels of
hazardous materials. Onsite samples (for example, soil, water, and materials
from drums or bulk storage tanks, obviously contaminated ponds, lagoons,
pools, and leachates from hazardous waste sites) are considered hazardous. A
distinction must be made between the two types of samples in order to:
Determine appropriate procedures for transportation of samples. If
there is any doubt, a sample should be considered hazardous and
shipped accordingly.
Protect the health and safety of laboratory personnel receiving the
samples. Special precautions are used at laboratories when samples
other than environmental samples are received.
The following section describes the packaging, labeling and shipping
requirements for these two sample types. Specific DOT regulations for hazardous
materials shipping papers and general marking requirements are presented as
Attachments C-1 and C-2.
ENVIRONMENTAL SAMPLES
Environmental samples must be packaged and shipped according to the
fo I Iowi ng procedures.
Packag i ng
Environmental samples may be packaged following the procedures outlined
later for samples classified as "flammable liquids" or "flammable solids," but
the requirements for marking, labeling, and shipping papers do not apply.
Environmental samples may also be packaged without being placed inside
metal cans as required for flammable liquids or solids.
Place sample container, properly identified and with a sealed lid,
in a polyethylene bag, and seal bag.
C-2
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Appendix C
Revision 0
Page 3 of 23
Place sample in a fiberboard container or metal picnic cooler which
has been lined with a large polyethylene bag.
Pack with enough noncombustible, absorbent, cushioning material to
minimize the possibility of the container breaking.
Seal large bag.
Seal or close outside container.
Mark!ng/Label ing
Sample containers must have a completed sample identification tag and the
outside container must be marked "Environmental Sample." The appropriate side
of the container must be marked "This End Up" and arrows placed accordingly.
No DOT marking or labeling are required.
Shipping Papers
No DOT shipping papers are required.
Transportation
There are no DOT restrictions on mode of transportation.
RATIONALE: HAZARDOUS MATERIAL SAMPLES
Samples not determined to be environmental samples or samples known or
expected to contain hazardous materials must be considered hazardous substance
samples and transported according to the following requirements:
If the substance in the sample is known or can be identified,
package, mark, label, and ship according to the specific
instructions for that material (if it is listed) in the DOT
Hazardous Materials Table, 49 CFR 172.101.
For samples of hazardous materials of unknown content, part 172.402
of 49 CFR allows the designation of hazard class based on the
shipper's knowledge of the material and selection of the appropriate
hazard class from part 173.2 (see Table C-l).
The correct shipping classification for an unknown sample is selected
through a process of elimination, utilizing the DOT classification system
(Table C-1). Unless known or demonstrated otherwise (through the use of
radiation survey instruments), the sample is considered radioactive and
appropriate shipping regulations for "radioactive material" followed. If
radioactive material is eliminated, the sample is considered to contain
"Poison A" materials (Table C-2), the next classification on the list. DOT
defines "Poison A" as extremely dangerous poisonous gases or liquids of such a
nature that a very small amount of gas, or vapor of the liquid, mixed with air
is dangerous to life. Q_3
-------
Appendix C
Revision 0
Page 4 of 23
TABLE C-1. DOT PRIORITY RANKING OF HAZARDOUS MATERIALS
Category
Definition
AppI i cat i on reguI at i ons
General
1 Radioactive Material
2 Poison A
3 Flammable Gas
4 Nonflammable Gas
5 Flammable Liquid
6 Oxidizer
7 Flammable Sol id
8 Corrosive Material (Liquid)
9 Poison B
10 Corrosive Material (Solid)
11 Irritating Materials
12 Combustible Liquid (in
containers exceeding 100
gal capacity)
13 ORM-B
14
-A
15 Combustible Liquid (in
containers having capacities
of 110 gal or less)
16 ORM-E
49 CFR 173.389
49 CFR 173.326
49 CFR 173.300
49 CFR 173.300
49 CFR 173.115
49 CFR 173.151
49 CFR 173.150
49 CFR 173.240
49 CFR 173.343
49 CFR 173.240
49 CFR 173.381
49 CFR 173.115
49 CFR 173.1-173.34, 177
49 CFR 173.390-173.398
49 CFR 173.327-173.337
49 CFR 173.300-173.316
49 CFR 173.300-173.316
49 CFR 173.116-173.119,
173.121-173.149a
49 CFR 173.152-173.239a
49 CFR 173.152-173.2393
49 CFR 173.241-173.2993
49 CFR 173.344-173.379
49 CFR 173.241-173.2993
49 CFR 173.381-173.385
49 CFR 173.116-173.1183,
173.121-173.1493
49 CFR 173.800 49 CFR 173.510, 173.800-
173.862
49 CFR 163.605 49 CFR 173.510, 173.605-
173.655
49 CFR 173.115 49 CFR 173.116-173.1183,
173.121-173.1493
49 CFR 173.1300 49 CFR 173.510
C-4
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Appendix C
Revision 0
Page 5 of 23
TABLE C-2. DOT LIST OF CLASS "A" POISONS (49 CFR 172.101)
Phys i caI state at
Material standard temperature
Arsine Gas
Bromoacetone Liquid
Chloropicrin and methyl chloride mixture Gas
Chloropicrin and nonflammable, nonliquified compressed Gas
gas mixture
Cyanogen chloride Gas (13.TC)
Cyanogen gas Gas
Gas identification set Gas
Germane
Grenade (with Poison "A" gas charge)
Hexaethyl tetraphosphate/compressed gas mixture Gas
Hydrocyanic acid (prussic) solution Liquid
Hydrocyanic acid, liquified Gas
Insecticide liquified gas containing Poison "A" or Gas
Poison "B" material
Methyldichloroarsine Liquid
Nitric oxide Gas
Nitrogen peroxide Gas
Nitrogen tetroxide Gas
Nitrogen dioxide, liquid Gas
Parathion/compressed gas mixture Gas
Phosgene (diphosgene) Liquid
C-5
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Appendix C
Revision 0
Page 6 of 23
Most poison A materials are gases or compressed gases and would not be
found in drum-type containers. Liquid poison A's would be found only in
closed containers. All samples taken from closed drums do not have to be
shipped as poison A's, which provides for a "worst case" situation. Based
upon information available, a judgment must be made whether a sample from a
closed container is a poison A.
If poison A is eliminated as a shipment category, the next two
classifications are "flammable" or "nonflammable" gases. Since few gas
samples are collected, "flammable liquid" would be the next applicable
category. With the elimination of radioactive material, poison A, flammable
gas, and nonflammable gas, the sample can be classified as flammable liquid
(or solid) and shipped accordingly. These procedures would also suffice for
shipping any other samples classified below flammable liquids in the DOT
classification table.
For samples containing unknown material, other categories listed below
flammable liquids/solids on the table are generally not considered because
eliminating other substances as flammable liquids requires flashpoint testing,
which may be impractical and possibly dangerous at a site. Thus, unless the
sample is known to consist of material listed below flammable liquid on the
table, it is considered a flammable liquid (or solid) and shipped as such.
PROCEDURES: SAMPLES CLASSIFIED AS FLAMMABLE LIQUID (OR SOLID)
The following procedure is designed to meet the requirements for a
"limited quantity" exclusion for shipment of flammable liquids and solids, as
set forth in parts 173.118 and 173.153 of 49 CFR. By meeting these
requirements, the DOT constraints on packaging are greatly reduced. Packaging
according to the limited quantity exclusion requires notification on the
shipping papers.
Packag ing
1. Collect sample in a glass container (16 ounces or less) with
a nonmetallic, teflon-lined screw cap. To prevent leakage, fill
container no more than 90 percent full at 130°F. If an air space in
the sample container would affect sample integrity, place that
container within a second container to meet 90 percent requirement.
2, Complete sample identification tag and attach securely to sample
conta iner.
3. Seal container and place in 2-mi I thick (or thicker) polyethylene
bag, one sample per bag. Position identification tag so it can be
read through bag. Seal bag.
4, Place sealed bag inside metal can and cushion it with enough
noncombustible, absorbent material (for example, vermiculite or
diatomaceous earth) between the bottom and sides of the can and bag
C-6
-------
Appendix C
Revision 0
page 7 of 23
to prevent breakage and to absorb leakage. Pack one bag per can. Use
clips, tape, or other positive means to hold can lid securely,
tightly, and permanently.
5, Place one or more metal cans into a strong outside container, such
as a metal picnic cooler or a DOT approved fiberboard box. Surround
cans with noncombustible, absorbent, cushioning material for
stability during transport.
6, Limited quantities of flammable liquids, for the purpose of the
exclusion, are defined as one pint or less (49 CFR part
7, Limited quantities of flammable solids, for the purpose of this
exclusion, are defined as one pound net weight in inner containers
and no greater than 25 pounds net weight in the outer container
(49 CFR part 173.153(a)(I)) .
Marking/Label ing
1, Use abbreviations only where specified.
2, Place following information, either hand printed or in label form,
on the metal card.
Laboratory Name and Address
"Flammable Liquid, n.o.s. UN1993" or "Flammable Solid, n.o.s.
UN1325."
Not otherwise specified (n.o.s.) is not used if the flammable liquid
(or solid) is identified. Then the name of the specific material is
listed before the category (for example, Acetone, Flammable Liquid)
followed by its appropriate UN number found in the DOT hazardous
materials table (172.101).
3, Place the following DOT labels (if applicable) on outside of can (or
bottle).
"Flammable Liquid" or "Flammable Solid."
"Dangerous When Wet." Must be used with "Flammable Solid" label
if material meets the definition of a water-reactive material.
"Cargo Aircraft Only." Must be used if net quantity of sample
in each outer container is greater than 1 quart (for "Flammable
Liquid, n.o.s.") or 25 pounds (for "Flammable Solid, n.o.s.)."
4, Place all information on outside shipping container as on can (or
bottle), specificaIly,
C-7
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Appendix C
Rev i s i on 0
page 8 of 23
Proper shipping name.
UN or NA number.
t Proper label(s).
Addressee and addresser.
(Note that the previous two steps (2 and 3) are EPA
recommendat i ons. Step 4 i s a DOT requ i rement.
5, Print "Laboratory Samples and "This End Up" or "This Side Up"
clearly on top of shipping container. Put upward pointing arrows on
all four sides of container.
Shipping Papers
1. Use abbreviations only where specified.
Complete carrier-provided bill of lading and sign certification
statement (if carrier does not provide, use standard industry
form). Provide the following information in the order listed. (One
form may be used for more than one exterior container.)
"Flammable Liquid, n.o.s. UN1993" or "Flammable Solid, n.o.s.
UN1325."
"Limited Quantity" (or "Ltd. Qty.").
Net weight or net volume (weight or volume may be abbreviated)
just before or just after "Flammable Liquid, n.o.s. UN1325" or
"Flammable Solid, n.o.s. UN1325"
Further descriptions such as "Laboratory Samples" or "Cargo
Aircraft Only" (if applicable) are allowed if they do not
contradict required information.
3, Include chain-of-custody record, properly executed, in outside
container if legal use of samples is required or anticipated.
Transportation
1. Transport unknown hazardous substance samples classified as
flammable liquids by rented or common carrier truck, railroad, or
express overnight package services.
2, Do not transport by any passenger-carrying air transport system,
even if they have cargo only aircraft. DOT regulations permit
regular airline cargo only aircraft, but difficulties with most
suggest avoiding them. Instead, ship by airlines that only carry
cargo. c_g
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3, Transport by government-owned vehicle, including aircraft. DOT
regulations do not apply, but EPA personnel will still use
procedures described except for execution of the bill of lading with
certification.
Other Considerations
1. Check with analytical laboratory for size of sample to be collected
and if sample should be preserved or packed in ice.
2, For EPA employees, accompany shipping containers to carrier and, if
required, open outside container(s) for inspection.
3, For overnight package services, determine weight restrict ions--at
least One service limits weight to 70 pounds per package.
PROCEDURES: SAMPLES CLASSIFIED AS POISON "A"
Packaging
1. Collect samples in a polyethylene or glass container with an outer
diameter narrower than the valve hole on a DOT specification No. 3A1800
or No. 3AA1800 metal cylinder. To prevent leakage, fill container no
more than 90 percent full (at 130°F).
2, Seal sample container.
3, Complete sample identification tag and attach securely to sample
container.
4, Attach string or flexible wire to neck of the sample container;
lower it into metal cylinder partially filled with noncombustible,
absorbent cushioning material (for example, diatomaceous earth or
vermicul ite). Place only one container in a metal cylinder. Pack
with enough absorbing material between the bottom and sides of the
sample container and the metal cylinder to prevent breakage and
absorb leakage. After the cushioning material is in place, drop the
end of the string or wire into the cylinder valve hole.
5, Replace valve, torque to 250 ft/lb (for I-inch opening), and replace
valve protector on metal cylinder, using Teflon tape.
6, Place one or more cylinders in a sturdy outside container.
Marking/Label ing
1. Use abbreviations only where specified.
2, Place following information, either hand printed or in label form, on
the side of the cylinder or on a tag wired to the cylinder valve
protector. Q_g
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"Poisonous Liquid, n.o.s. NA1955" or "Poisonous Gas, n.o.s.
NA1955."
Laboratory name and address.
t DOT label "Poisonous Gas" (even if sample is liquid) on
cyl inder.
3, Put all information on metal cylinder on outside container.
4, Print "Laboratory Sample" and "Inside Packages Comply With
Prescribed Specifications" on top and/or front of outside
container. Mark "This Side Up" on top of contaner and
upward-pointing arrows on all four sides.
Shipping Papers
1. Use abbreviations only as specified.
2, Complete carrier-provided bill of lading and sign certification
statement (if carrier does not provide, use standard industry
form). Provide following information in order listed. (One form
may be used for more than one exterior container.)
"Poisonous Liquid, n.o.s. NA1955."
Net weight or net volume (weight or volume may be abbreviated),
just before or just after "Poisonous Liquid, n.o.s. NA1955."
3, Include a chain-of-custody record, properly executed, in container
or with cylinder if legal use of samples is required or anticipated.
4, For EPA employees, accompany shipping container to carrier and, if
required, open outside container(s) for inspection.
Transportation
1. Transport unknown hazardous substance samples classified as poison A
only by ground transport or Government-owned aircraft. Do not use
air cargo, other common carrier aircraft, or rented aircraft.
SAMPLE IDENTIFICATION
The sample tag is the means for identifying and recording the sample and
the pertinent information about it. The sample tag should be legibly written
and completed with an indelible pencil or waterproof ink. The information
should also be recorded in a logbook. The tag should be firmly affixed to the
sample container. As a minimum, it should include:
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§ Exact location of sample.
T i me and date samp Ie was coI Iected.
Name of sampler and witnesses (if necessary).
Project codes, sample station, number, and identifying code (if
appl icable).
Type of sample (if known).
Hazardous substance or environmental sample.
Tag number (if sequential tag system is used).
Laboratory number (if applicable).
Any other pertinent information.
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ATTACHMENT C-1 Appendix C
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US Deportment GUIDE FOR page 12 of 23
*KX*tyMy%jtfffim^
JJlSJJ^Jlan, HAZARDOUS MATERIALS SHIPPING PAPERS -
Ad»*iittiuHun
The following information has been abstracted from the Code of Federa Regulations, Title 49,
Parts 100-177
1. DEFINITIONS
A. SH PPING PAPER (Sec. 171.8) A shipping paper may be a shipping order, bi of lading,
manifest, or other shipping document serving a similar purpose containing the information
required by Sec. 172.202, 172.203 and 172.204.
HAZARDOUS WASTE MAN FEST (CFR. Tit e 40, Sec. 262.20) A hazardous waste manifest is a
document (shipping paper) on which all hazardous waste is identified. A copy of the
manifest must accompany each shipment of waste from the point of pick-up to the destination.
(CFR, Title 49, Sec. 172.205)
2. SHIPPERS RESPONSIBILITY [Sec. 172.200(a)] The shipper has the responsibility to properly
prepare the shipping paper when offering a hazardous material for transport.
NOTE: For shipments of hazardous waste, the hazardous waste manifest is the only authorized
documentation. (CFR, Title 40, Sec. 262.23)
3. HAZARDOUS MATERIALS DESCRIPTION (Sec. 172.202) The shipping description of a hazardous
materia on a shipping paper must nclude the following information:
A. Proper shipping name- Sec. 172.101 or Sec. 172.102 (when authorized);
B. The hazard class prescribed for the material in the same section; [See exceptions
Sec. 172.202(a)(2)].
C. The Identification number for the material (preceded by "UN" or "NA" as appropriate); and
D. Except for empty packagings, the total quantity (by weight, volume, or as otherwise
appropriate) of the hazardous materials covered by the description.
E. Except as otherwise provided in the regulations, the basic description in 3A, B and C
above must be shown in sequence. For example "Acetone, Flammable Liquid, UN1090."
F. The total quantity of the material covered by one description must appear before or. after
(or both before and after) the basic description as indicated in 3A, B end C above.
(I) Abbrev i at i ons may be used to spec i fy the type of packag i ng, we i ght or voIume.
Example: "40 Cyl . Nitrogen Nonflammable gas UN 1066, 800 pounds"; "1 box Cement
liquid, n.o.s., Flammable iquid, NAM33, 25 bs."
(2) Type of packaging and destination marks may be entered in any appropriate manner
before or after the basic description.
G. Technical and chemical group names may be entered in parentheses between the proper
shipping name and hazard class. Example: Corrosive liquid, n.o.s. (capryrl chloride),
corrosive material .
GENERAL ENTRIES ON SHIPPING PAPERS (Sec. 172.201)
A. CONTENTS When describing a hazardous material on the shipping paper(s), that description
must conform to the following requirements:
(1) When a hazardous material, including materials not subject to the regulations, is
described on the same shipping paper, the hazardous materia description entries
required by Sec. 172.202 and those additiona entries that may be required by
Sec. 172.203.
a. Must be entered first (See Figure 1), or
b. Must be entered in a contrasting color, except that a description on a repro-
duction of a shipping paper may be highlighted, rather than printed, in a
contrasting color (these requirments apply only to the basic description
required by Sec. 172.202(a)(I), (2) and (3), (See Figure 1); or
c. Must be identified by the entry "X" placed before the proper shipping name in a
column captioned "HM" [the "X" may be replaced by "RQ"' (Reportable Quantity),
if appropriate] See Figure 1.
(2) The required shipping description on a shipping paper and all copies that are used
for transportation purposes must be legible and printed (manually or mechanically)
in Engl ish.
(3) Unless it is specifically authorized or required, the required shipping description
may not contain any code or abbreviation.
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(4) A shipping paper may contain additiona information concerning the material provided
the information is not inconsistent with the required description. Unless otherwise
permitted or required, additional information must be placed after the basic descrip-
tion required bv Sec. 172.202(a).
a. When appropriate, the entries "IMCO" or "IMCO Class" may be entered immediately
before or immediately following the class entry in the basic description.
b. fa materia meets the definition of more then one hazard c ass, the additional
hazard class or classes may be entered after the hazard class in the basic
description.
OF SH PPER A shipping paper for a shipment by water must contain the name of the
shipper.
ADDITIONAL DESCRIPTION RFOUIREMENTS (Sec. 172.2031 (ALL MODES')
A. Exempt i ons - Each shipping paper issued in connection with a shipment made under an
exemptiom must bear the notation "DOT-E" followed by the exemption number assigned
(Example: DOT-E 4648) and so located that the exemption number is c early associated with
the description to which the exemption applies.
B. Limited Quantities - Descriptions for materials defined as "Limited Quantities" ...must
include the words "Limited Quantities" or "Ltd. Qty." following the basic description.
C. Hazardous Substances
(1) If the proper shipping name for a mixture or solution that is a hazardous substance
does not identify the constituents, making it a hazardous substance, the name or names
of such constituents shall be entered in association with the basic description.
(2) The letters "RQ" (Reportable Quantity) shajl be entered on the shipping paper either
before or after the basic description required by Sec. 172.202 for each hazardous
substance. (See definition Sec. 171.8) Example: RQ, Cresol, Corrosive Material,
NA2076; or Adipic Acid, ORM-E, NA9077, RQ.
D. Radioactive Materials - For additional description for radioactive materials, refer to
Sec. 172.203(d).
E. Empty Packag i ngs
(1) Except "for a tank car, or any packaging that still contains a hazardous substance,
the description on the shipping paper for an empty packaging containing the residue
of a hazardous materia may include the word(s) "EMPTY" or "EMPTY: Last Contained
(Name of Substance)" as appropriate in association with the basic description of the
hazardous materia last contained in the packaging.
(2) For empty tank cars, see Sec. 174.25(c).
(3) If a packaging, including a tank car, contains a residue that is a hazardous substance
the description on the snipping paper shall be prefaced with the phrase "EMPTY: Last
Contained (Name of Substance)" and shall have "RQ" entered before or after the basic
description.
F. Dangerous When Wet - The words "Dangerous When Wet" shall be entered on the shipping paper
in association with the basic description when a package covered by the basic description
is required to be labeled with a "DANGEROUS WHEN WET" label.
G. Poisonous Materia s - Notwithstanding the c ass to which a material is assigned:
(1) If the name of the compound or principal constituent that causes the material to meet
the definition of a poison is not included in the proper shipping name for the
material, the name of that compound or constituent shall be entered on the shipping
paper in association with the shipping description for the material.
(2) The name of the compound or principal constituent may be either a technical name or
any name for the material that is listed in the NIOSH Registry. (Reg istry of Toxic
Effects of Chemical Substances. 1978 Edition) [Sec. 172.203(k)]
NOTE: For additional detai s, see Sec. 172.203(k)
Exceptions: OTHER REGULATED MATERIAL (ORM-A, B, C, AND D)
(1) Shippimg paper requirements do not apply to any material other than a hazardous waste
or a hazardous substance that is:
a. An ORM-A, B or C unless it is offered or intended for transportation by air or
water when it is subject to the regulations pertaining to transportation by air or
water as specified in Sec. 172.101 (Hazardous Materials Table); or
b. An ORM-D unless it is offered or intended for transportation by air.
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MODAL REQUIREMENTS
(ADDITIONAL INFORMATION)
NOTE : In addition to the basic requirements for shipping papers, additiona information is
isted for each mode.
6. TRANSPORTATION BY RAIL
A. SHIPPING PAPERS (Sec. 176.24)
(1) Except as provided in paragraph (b) of this section, no person may accept for trans-
portation by rai any hazardous mater i a which is subject to this subchapter unless
he has received a shipping paper prepared in a manner specified in Sec. 172.200.
In addition, the shipping paper must include a certificate, if required by
Sec. 172.204. However, no member of the train crew of a train transporting the
hazardous material is required to have a shippers certificate on the shipping paper
in his possession if the original shipping paper containing the certificate is in
the originating carriers possession.
(2) This subpart does not apply to materials classed as ORM-A, B, C or D.
B. ADDITIONAL DESCRIPTION FOR SHIPPING PAPERS [Sec. 172.203(g)]
(1) The shipping paper for a rail car containing a hazardous material must contain the
notation "Placarded" followed by the name of the placard required for the rai car.
(2) The shipping paper for each specification DOT 112A or 114A tank car (without head
shields) containing a flammable compressed gas must contain the notation "DOT 112A"
or "DOT 114A", as appropriate, and either "Must be handled in accordance with
ERA E.O. No. 5" or "Shove to rest per E.O. No. 5."
NOTE: For additional detai s, refer to Part 174.
7. TRANSPORTATION BY AIR
A. SHIPPING PAPERS ABOARD AIRCRAFT (Sec. 175.35) A copy of the shipping papers required by
Sec. 175.30(a)(2) must accompany the shipment it covers during transportation aboard an
aircraft.
NOTE: The documents required (shipping papers and notification of pi lot-in-command) may be
combined into one document if it is given to the pi lot-in-command before departure
of the aircraft. [Sec. 175.35(b)].
B. NOTIFICATION OF PI LOT-IN-CQMMAND (Sec. 175.33) The operator of the aircraft shall give
the pi lot-in-command the following information in writing before takeoff (Sec. 175.35):
(1) Description of hazardous material on shipping papers (Sec. 172.202 and 172.203);
(2) Location of the hazardous material in the aircraft; and
(3) The results of the inspection requirements by Sec. 175.30(b).
NOTE: For additional details, refer to Part 175.
8. TRANSPORTATION BY WATER
A. SHIPPING PAPERS (Sec. 176.24) A carrier may not transport a hazardous material by vessel
unless the material is properly described on the shipping paper in the manner prescribed
in Part 172.
B. CERTIFICATE (Sec. 176.27)
(1) A carrier may not transport a hazardous material by vessel unless he has received a
certificate prepared in accordance with Sec. 172.204.
(2) In the case of an import or export shipment of hazardous materia s which will not be
transported by rail, highway, or air, the shipper may certify on the bill of lading or
other shipping paper that the hazardous material is properly classed, described,
marked, packaged and labeled according to Part 172 or in accordance with the require-
ments of the IMCO Code. (See Sec. 171.12)
c. DANGEROUS CARGO MANIFEST (Sec. 176.30) The master of a vessel transporting hazardous
materials or his authorized representative shall prepare a dangerous cargo manifest, list,
or stowage plan. This document may not include a material which is not subject to the
requirements of CFR, Title 49, or the IMCO Code. This document must be kept in a desig-
nated holder on or near the vessel's bridge. (See Sec. 176.30 for details)
D. EXEMPTIONS (Sec. 176.31) If a hazardous materia is being transported by vessel under the
authority of an exemption and a copy of the exemption is required to be on board the
vessel, it must be kept with the dangerous cargo manifest.
NOTE: For additional details, refer to Part 176.
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E. ADDITIONAL DESCRIPTION FOR SH PPING PAPERS [Sec. 172.203(1)
(1) Each shipment by water must have the following additional shipping paper entries:
a. Identification of the type of packages such as barrels, drums, cylinders, and
boxes,
b. The number of each type of packages including those in freight container or on
a pa et, and
c. The gross weight of each type of package or the individual gross weight of each
package.
(2) The shipping papers for a hazardous material offered for transportation by water to
any country outside the United States must have in parenthesis the technica name
of the material following the proper shipping name when the material is described
by a "n.o.s." entry in Sec. 172.101 (Hazardous Materials Table). For example:
Corrosive liquid, n.o.s. (caprylyl chloride), Corrosive material. However, for a
mixture, only the technical name of any hazardous material giving the mixture its
hazardous properties must be identified.
9. TRANSPORTATION BY HIGHWAY
A: SHIPPING PAPERS (Sec. 177.817)
(1) General - A carrier may not transport a hazardous material unless it is accompanied
by a shipping paper that is prepared in accordance with Sec. 172.201, 172.202 and
172.203.
(2) Shipper's certification - An initial carrier may not accept hazardous materials
offered for transportation unless the shipping paper describing the material in-
cludes a shipper's certification which meets the requirements in Sec. 172.204 of thi
subchapter. The certification is not required for shipments to be transported en-
tirely by private carnage and for bulk shipments to be transported in a cargo tank
supplied by the carrier. [Sec. 177.817(c)]
(3) Interlining with carriers by rail - A motor carrier shall mark on the shipping paper
required by this section, if it offers or de ivers a freight container or transport
vehicle to a rail carrier for further transportation: [Sec. 177.817(c)]
a. A description of the freight container or transport vehicle; and
b. The kind of placard affixed to the freight container or transport vehic e.
(4) This subpart does not apply to materials classed as an ORM-A, B, C or D.
(5) Accessibility of shipping papers: The driver and each carrier using the vehicle
shall ensure that the shipping paper is readily available and recognizable by
authorities in the case of an accident or inspection. [See Sec. 177.817(e) for
detai Is]
B. ADDITIONAL DESCRIPTION FOR SHIPPING PAPERS [Sec. 172.203(h)] For additional descriptions
for Anhydrous ammonia see Sec. 172.203(h)(I); Liquefied petroleum gas see
Sec. 172.203(h)(2) and Exemptions see Sec. 172.203(a).
10. SHIPPER'S CERTIFICATION (Sec. 172.204)
A. GENERAL (Except B and D below)
(1) Except as provided in paragraphs (b) and (c) of Sec. 172.204, each person who offers
a hazardous material for transportation shall certify that the material offered for
transportation is in accordance with the regulations by printing (manually or
mechanically) the following statement on the shipping paper containing the required
description:
This is to certify that the above-named materials are properly
classified, described, packaged, marked and labeled, and are in
proper condition for transportation according to the applicable
regulations of the Department of Transportation.*
The works "herein-named" may be substituted for the words "above named".
For hazardous waste shipments, the words "and the EPA" must be added to the
end of the certification. [See CFR, Title 40, Sec. 262.21 (b)]
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B. AIR TRANSPORTATION
(1) General - Certification containing the following language may be used in place of
the certification required by paragraph A(1) above:
I hereby certify that the contents of this consignment are fully
and accurately described above by proper shipping name and are
classified, packed, marked and labeled, and in proper condition
for carriage by air according to applicable national governmental
regulations.
(2) Pup I icate Certificate - Each person who offers a hazardous material to an aircraft
operator for transportation by air shall provide two (2) copies of the certificate.
(Sec. 175.30)
(3) Passenger and Cargo Aircraft - If hazardous materials are offered for transportation
by air, add to the certificate the following statement:
This shipment is with in the limitations prescribed for passenger/
cargo-only aircraft, (delete non-applicable)
(4) Radioactive Material - Each person who offers any radioactive material for trans-
portation aboard a passenger-carrying aircraft shall sign (mechanically or manually)
a printed certificate stating that the shipment contains radioactive material in-
tended for use in, or incident to, research, medical diagnosis or treatment.
NOTE: See Sec. 175.10 for exceptions.
C. SIGNATURE - The certifications required above must be legibly signed (mechanically or
manua ly) by a principa , officer, partner or employee of the shipper or his agent.
[Sec. 172.204(d)]
EXCEPTIONS - Except for a hazardous waste, no certification is required for hazardous
material offered for transportation by motor vehicle and transported:
1} In a cargo tank supplied by the carrier, or
2) By the shipper as a private carrier except for hazardous material that is to be
reshipped or transferred from one carrier to another.
(3) No certification is required for the return of an empty tank car which previously
contained a hazardous material and which has not been cleaned or purged.
HAZARDOUS WASTE MANIFEST INFORMATION
The following information has been abstracted from the Code of Federal Regulations (CFR),
Tit e 49, Parts 100-177 and CFR, Tit e 40, Part 262.
1. DEFINITIONS
A. HAZARDOUS WASTE MANIFEST (CFR Title 40, §262.20)
A hazardous waste manifest is a shipping document on which all hazardous wastes are
identified.
B. SHIPPING PAPER - A shipping order, bill of lading, manifest, or other shipping
document serving a similar purpose and containing the information required by
§172.202, §172.203 and §172.204.
DOT HAZARDOUS MATERIALS MANIFEST REQUIREMENTS (§172.205)
No person may offer, transport, transfer or del iver a hazardous waste unless a
hazardous waste manifest is prepared, signed, carried and given as required of that
person by §172.205.
B. The shipper (generator) must prepare the manifest in accordance with the EPA
Regulations, CFR Tit e 40, Part 262.
C. The original copy of the manifest must be dated by, and bear the handwritten signa-
ture of the person representing the:
(1) Shipper (generator) of waste at the time it is offered for transportation, and
(2) Initial carrier accepting the waste for transportation.
D. A copy of the manifest must be dated by, and bear the handwritten signature of the
person representing:
(1) Each subsequent carrier accepting the waste for transportation, at the time of
acceptance, and
(2) The designated facility receiving the waste, upon receipt.
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E. A copy of the manifest bearing all required dates and signatures must be:
(1) Given to a person representing each carrier accepting the waste for transportation,
(2) Carried during transportation in the same manner as required for shipping papers,
(3) Given to a person representing the designated facility receiving the waste,
(4) Returned to the shipper (generator) by the carrier that transported the waste from
the United States to a foreign destination with a notation of the date of departure
from the United States, and
(5) Retained by the shipper (generator) and by the initial and each subsequent carrier
for three (3) years from the date the waste was accepted by the initial carrier.
Each retained copy must bear all required signatures and dates up to and inc uding
those entered by the next person who received the waste.
F. The requirements of §172.205(d) and (3) do not apply to a rail carrier when waste is
delivered to a designated facility by railroad if:
(1) AI I of the information required to be entered on the manifest (except generator
and carrier identification numbers and the generator's certification) is entered
on the shipping paper carried in accordance with §174.26(c);
(2) The delivering rai carrier obtains and retains a receipt for the waste that is
dated by and bears the handwritten signature of the person representing the
designated facility; and
(3) A copy of the shipping paper is retained for three (3) years by each railroad
transporting the waste.
G. The person delivering a hazardous waste to an initia rail carrier sha send a copy of
the manifest, dated and signed by a representative of the rail carrier, to the person
representing the designated facility.
H. A hazardous waste manifest required by CFR, Title 40, Part 262 containing all the infor-
mation required by CFR, Title 49, Subpart C, may be used as the shipping paper.
3. THE MANIFEST-GENERAL REQUIRMENTS (§262.20)
A. A generator (shipper) who transports, or offers for transportation, hazardous waste
for off-site treatment, storage, or disposal must prepare a manifest before transporting
the waste off-site.
B. A generator (shipper) must designate on the manifest one facility which is permitted to
hand e the waste described on the manifest.
C. A generator (shipper) may also designate on the manifest one alternate facility which
i s perm i tted to hand Ie h i s waste i n the event an emergency prevents deI i very of the
waste to the primary designated facility.
D. If the transporter (carrier) is unable to del iver the waste to the designated faci I ity,
the generator must either designate another faci I ity or instruct the transporter to
return the waste.
4. MANIFEST INFORMATION (§262.21)
A~I he manifest must contain:
m Manifest document number;
(2) Generator's (Shipper's) name, mailing address, telephone number, and the EPA
identification number;
(3) Name end EPA identification number of each transporter (carrier);
(4) Name, address and EPA identification number of the designated faci ity and an
alternate facility, if any;
(5) Description of the waste(s) (e.g. proper shipping name required by the Department
of Transportation Hazardous Naterials Regulations CFR, Title 49, §172.101,
§172.202 and §172.203); and
(6) Tota quantity of each hazardous waste by units of weight or volume, and the type
and stir of containers loaded into or onto the transport vehicle.
B. Certification [§262.21 (b)] The following certification must appear on the manifest:
"This is to certify that the above named materials are properly classified, described,
packaged, marked, labeled and are in proper condition for transportation according
to the applicable regulations of the Department of Transportation and the EPA"
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COPIES OF MANIFEST REQURED (§262.22)
I he manifest must consist of at least the number of copies to provide the generator, each
transporter, and the owner or operator of the designated facility with one copy each for
their records and another copy to be returned to the generator.
USE OF THE
FEST (§262.23)
A. The generator must:
(1) Sign the manifest certification by hand;
(2) obtain the handwritten signature of the initial transporter and date of acceptance
of manifest; and
(3) Retain one copy in accordance with §262.40(a).
B. The generator must give the transporter the remaining copies of the manifest.
C. Shipment of hazardous waste within the United States solely by railroad or water (bulk
shipments only); the generator must send three (3) copies of the manifest dated and
signed in accordance with §262.20 to the owner or operator of the designated faci ity.
NOTE: Copies of the manifest are not required for each transporter. For special
provisisions for rail or water (bu k shipment) transporters see §263.20(e).
PREPARATION OF HAZARDOUS WASTE FOR SHIPMENT (§262.30)
^ Packaging Hazardous Waste - The generator (shipper) has the responsibility for the
classification and packaging of hazardous waste prior to offering for transportation.
The requirements for packaging wi I I be found in the Department of Transportation
Regulations CFR, Title 49, Parts 172, 173, 178 and 179.
B. Labe
nq Requirements (§262.31) - Prior to offering a hazardous waste for transportation
enerator (shipper) must label each package in accordance with CFR Title
off-site, the
49, Part 172, Subpart E
Marking Requirements (§262.32) - Prior to offering hazardous waste for transportation
off-site, the generator must:
Mark each package of the hazardous waste; and
Mark each container 110 gallons or less offered for transportation with the
following words and information displayed in accordance with the requirements
of CFR, Title 69, Sec. 172.304.
"HAZARDOUS WASTE-Federal Law Prohibits Improper Disposal. If found,
contact the nearest pol ice or pub I ic safety authority or the United
States Environmental Protection Agency"
Generator's Name and Addrees
Manifest Document Number
D. Placarding Requirements (§262.33) - Prior to offering a hazardous waste for transporta-
tion off-site, the generator must:
(1) Placard the shipment; or
(2) Offer the initial transporter (carrier) the appropriate placards. (CFR Title 49,
Part 172, Subpart F)
NOTE: This handout is designed as a training aid only. It does not relieve persons from comply-
ing with the Department of Transportation's Hazardous Materia s Regulations. Final
authority for use of shipping papers is found in the Code of Federal Regulation, Title 49,
Part 100-177.
NOTE: This material may be reproduced without special permission from this office. Any comments
or recommendations should be sent to the address below.
DEPARTMENT OF TRANSPORTATION
RESEARCH AND SPECIAL PROGRAMS ADMINISTRATION
MATERIALS TRANSPORTATION BUREAU
OFFICE OF OPERATIONS AND ENFORCEMENT
INFORMATION SERVICES DIVISION, DMT-11
WASHINGTON, D.C. 20590
REVISED MAY 1981
C-19
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US Department
of Ian
ATTACHMENT C-2
Meseovcn ono
Special Programs
Administration
GUIDE FOR MARKINGS
Appendix C
Rev i s i on 0
Page 20 of 23
The following information has been abstracted from the Code of Federal Regulations
(CFR), Title 49 Transportation, Parts 100-199. Refer to the appropriate Sections
for detai Is.
NOTE : Rulemaking proposals are outstanding or are contemplated concerning the
regulations. Keep up to date with the changes.
MARKING - means the application of the descriptive name, proper shipping name,
hazard class, identification number (when authorized), instructions, cautions,
weight or a combination thereof on the outstde shipping container. Marking also
includes the specification mark for both the inside and outside shipping con-
tainers required by the Hazardous Materials Regulation.
DESCRIPTIVE INFORMATION
GENERAL REQUIREMENTS (§172.300-172.304)
All containers of hazardous materials, i.e.
packages, freight containers, or transport
vehicles, must, unless specifically exempted,
be marked with the proper shipping name(s)
of the contents and the name and address
or either the consignee or consignor. All
markings must be:
1. Durable, in English, and printed on or
affixed to the surface of the package or
on a label, tag or sign.
2. On a background of a sharply contrasting
color and unobscured by labels or attach-
ments.
Antimony Chloride, Solid
To: Johnson Products Co.
1420 Main St.
Armstrong. AK 52650
3. Away from other markings that could reduce
i ts effect i veness.
LIQUIDS - INSIDE CONTAINERS (§172.312)
1. Inside containers must be packed with
closures in the upright position.
2. Must be marked on the outside with
"THIS END UP" or "THIS SIDE UP"
3. Arrows must be used only to show orienta-
tion of package. An arrow symbol indicated
by ANSI Standard MH6.11968 "THIS WAY UP".
Pictorial (arrows) of goods is recommended.
CorrosrV* Liquid. N.O.S.
'Johnson Product*
1420 Mtin St
'Armstrong, AK
52650
THIS SIDE UP
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Append i x C
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EXPORT BY WATER (§172.302)
All n.o.s. entries, when authorized in §172.101
or §172.102, must have the technical name(s) of
the material immediately following the proper
shipping name for export by water. For mixtures
(two or more) hazardous materials, the technical
name of at least two components must be identified.
RADIOACTIVE MATERIALS (§172.310)
1. Containers weighing over 110 pounds (gross
weight) must be marked on the container.
2. Must be marked "TYPE A" or "TYPE B" as
required in letters at least 1/2" high.
3. For export, the letters "USA" must follow
the specification markings or package
certification.
Corrosive Liquid, N.O.S.
(Phosphoric Acid)
Johnson Products Co.
1420 Rue D« La M»m
Nica, Franca
ran rtir'trrt "m~rr
6. W.I
TVw . U.S>J«Ma/SI
To: JOMMX *«dun Co.
OTHER REGULATED MATERIALS fORM'S) (§172.316)
ORM materials must be designated immediately
following or below the proper shipping name
marking within a rectangular border approxi-
mately 1/4 inch larger on each side of the
designation. The appropriate designation must
be one of the following:
1 .
2.
3.
4.
ORM-A
ORM-B -KEEP
ORM-B
ORM-C
5. ORM-D
DRY 6. ORM-D-AIR
7. ORM-E
OP»a_MatariaJ
| OBM-C |
To: Johnson Products Co.
1420 Main St
AK
52450
NOTE: These markings serve as the certifica-
tion by the shipper that the material is prop-
erly described, classed, packaged, marked and
labeled (when appropriate) and in proper con-
dition for transportation. Use of this type of
certification does not preclude the requirement
for a certificate on the shipping paper [§172.316(cX
AUTHORIZED CONTAINERS IN OUTSIDE CONTAINERS
OftM-0 KEEP DRY
EXAMPLE
When a DOT specification container is required for a hazardous material and that
container is overpacked in another container meeting the requirements of §173.21
and §173.24, the outside container must be marked in accordance with §173.25.
EXAMPLES: "THIS SIDE UP" or "THIS END UP" or "INSIDE PACKAGES COMPLY WITH
PRESCRIBED SPECIFICATIONS"
CYLINDERS - All cylinders must be marked in accordance with §173.34 and §§173.301
through 173.306. Cylinders passing re inspect ion and retesting must be marked in
accordance with §173.34(e)(6).
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Appendix C
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PORTABLE TANKS (§172.326 and §172.332) - Portable tanks must display the proper
shipping name in letters at least 2 inches high and placed on two opposite sides.
Identification numbers [§§171.101 and 171.102 (when authorized)] are required on
each side and each end for capacities of 1.000 gallons or more and on two opposing
sides in association with the proper shipping name for capacities of less than
1,000 gallons. The name of the owner or lessee must be displayed. Tanks carrying
compressed gases (DOT-51) must have all inlets and outlets, except safety relief
valves, marked to designate whether or not they communicate with vapor or liquid.
[§178.245-6(b)].
NOTE: When different hazardous materials are transported in marked portable tanks,
the shipping name and the identification number displayed must identify the material.
CARGO TANKS - HIGHWAY (COMPRESSED GASES) (§172.328) - Cargo tanks must be marked, in
letters no less than 2 inches high, with either the proper shipping name of the gas
or an appropriate common name, such as "Refrigerant Gas". Cargo tanks must only be
marked, i.e. proper shipping name and identification number [when authorized
(§§171.101 and 171.102)] for the material contained therein. DOT MC 331 tanks must
have inlets and outlets, except safety relief valves, marked to designate whether
they communicate with I iquid or vapor when the tank is fi I led to its maximum per-
mitted silling density. [§178.337-9(c)] .
TANK CARS - RAIL (§172.330) - Tank cars, when required to be marked with the proper
shipping name by Parts 173 and 179, must be marked in letters at least 4 inches high
with at least 5/8 inch stroke with the proper shipping name or the appropriate common
name. Identification number markings (when authorized) must be displayed on each side
and each end [§§171.101 and 171.102 (when authorized)]. Tank cars must only be
marked for the material contained therein.
NOTE: See referenced Sections for requirements for DOT-106 and DOT 110 tank car tanks.
EXAMPLE OF PLACARD AND PANEL WITH IDENTIFICATION NUMBER
1090
NOTE: The Identification Number (ID No.) may be displayed on placards or on
orange panels on tanks. Check the sides of the transport vehicle if the ID
number is not displayed on the ends of the vehicle.
OTHER MARKING REQUIREMENTS
REQUALIFIED CONTAINERS - Reusable cylinders, portable tanks, cargo tanks and tank
cars are required to be either visually inspected or retested at periodic intervals.
When this is accompl ished, the date of the requal ification must be shown on the
container as required in §§173.24, 173.31, 173.32, 173.33 and 173.34.
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Appendix C
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REUSE OF CONTAINERS - Some steel containers in the DOT Series (DOT-17C, 17E and 17H)
may be qua I ifled for reuse by a reconditioner of drums who is registered with the
Department of Transportation. These drums must meet the requirements of §173.28(m)
i.e. old labels removed, exemption number (if any) and descriptive markings removed
and the drum reconditioned. Other containers may be reused under varying conditions.
See §173.28 for detai Is.
CARGO HEATERS - Cargo heaters authorized for use with flammable liquid or gas must be
marked in accordance with §177.834(1)(2)(e) and (f).
MOTOR VEHICLES - Marking of motor vehicles and special requirements are found in
§§177.823 and 177.824.
SPECIFICATION CONTAINERS
Markings on specification containers must generally identify: (1) the DOT specifica-
tion number to which the container is made (Parts 178 and 179); (2) the manufacturers
name and address or symbol (registered with the Associate Director for the Office of
Hazardous Material Regulation). Duplicate symbols are not authorized. All containers
must comply with the marking requirements of §173.24 and the appropriate Section(s)
of Parts 178 and 179. Exceptions for Canadian and other import/export situations
may be found in §§171.12 and 173.8.
NOTE: For certain containers, specific detailed information such as original test
date information and type of material which may be required can be found in
Parts 178 and 179.
This publication does not contain all the marking requirements. It is designed as a
guide only. For details for all markings, consult Code of Federal Regulations, Title
49, Parts 100-199.
This publication may be reproduced without special permission from this office.
Department of Transportation
Research and Special Programs Administration
Materials Transportation Bureau
Office of Operation and Enforcement
Information Services Division, DMT-11
Washington, D.C. 20590
Revised September 1981
C-23
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Appendix D
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APPENDIX D
DOCUMENT CONTROL/CHAIN-OF-CUSTODY PROCEDURES
D-
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Appendix D
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Page 2 of 11
GENERAL
Adherence to strict document control and chain-of-custody procedures is
extremely important especially in relation to surveys at hazardous waste
sites. The legal implications alone demand that accountability be given an
utmost priority. The basic aspects of document control and chain-of-custody
have therefore been included in this section. For additional information, the
following publication, from which this section was developed, should be
consuI ted.
NEIC Policies and Procedures Manual, EPA-330-78-001R, May 1978
(revised December 1981), Section II
DOCUMENT CONTROL
The purpose of document control is to assure all project documents will
be accounted for when the project is complete. Document control should
include the use of serialized documents, a document inventory procedure and an
adequate document filing system, all issued by, under the control of, and
maintained by an appointed Document Control Officer (DCO). Table D-1 lists
the principal items subject to document control during a specific project.
Serialized Documents
Sample collection and analytical tags, and chain-of-custody records
should have preprinted serial numbers. It is not necessary that a sample tag
number match a custody record number, however, it is necessary that all issued
numbers be appropriately accounted for by the DCO. It is also necessary that
in the event a tag or custody record is damaged, lost or destroyed prior to
its use, its serial number and disposition are recorded.
Other Documents
Other documents used during the conduct of a project (e.g., field
logbooks, laboratory notebooks, data sheets, etc.) should be appropriately
coded with a unique identifier to ensure accountability. The project DCO will
be responsible for development of the document identification system, paying
particular attention to its utility and consistency for the specified
program. An example of a document identification system is as follows:
Subcontractor Code
Project Code (if necessary) Document Code Serial Number
00-000-000- -00- -A- -00001
In addition, a listing of suggested codes is shown in Table D-2.
D-2
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Appendix D
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Page 3 of 11
TABLE D-1 . DOCUMENTS SUBJECT TO CONTROL
Project Work Plan
Project Logbooks
Field Logbooks
Samp Ie Data Sheets
Sample Tags
Chain-of-Custody Records
Laboratory Logbooks
Laboratory Data, Calculations, Graphs, etc.
Sample Checkout
Sample Inventory
InternaI Memos
External Written Communication
Confidential Information
Photographs, Drawings, Maps
Quality Assurance Plan
Litigation Document
Final Report
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Appendix D
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Page 4 of 11
TABLE D-2. SUGGESTED DOCUMENT CODES
Document Code letter
Project Work Plans A
Project Logbooks B
Samp I ing Logbooks C
Sampling Data Sheets D1, D2 etc.
Samp I ing Coding Form E
Laboratory Notebooks G
Laboratory Data Sheets H1, H2 etc.
Sample Logs LI, L2 etc.
InternaI Memos M
External Written Communication N
Confidential Information 0
Photos, Maps, Drawings P
QA Plan Q
Reports R
Final Report FR
Mi see Ilaneous X
D-4
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Appendix D
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Page 5 of 11
CHAIN-OF-CUSTODY
The primary need for the implementation of chain-of-custody procedures
stems from the possibility that a sample or a piece of data derived from the
collection of a sample will be used as physical evidence in an enforcement
action. The purpose of chain-of-custody in these instances is to trace the
possession of a sample from the time of collection, until it or the derived
data is introduced as evidence in legal proceedings. Custody records should,
therefore, trace a sample from its collection, through all transfers of
custody, until it is delivered to the analytical laboratory. At this point,
internal laboratory records should document sample custody until its final
d isposition.
In order to establish that a sample is valid, it is also necessary to
document the measures taken to prevent and/or detect tamper ing--either to the
sample itself, the sampling equipment used or the environment sampled. This
is done by the use of evidence tape, locks and custody seals, and documented
entries noting their condition in field and laboratory log books. The custody
record must document any tampering that may have occurred; the absence of any
such comments indicates no tampering observed or noticed during the period of
custody.
Since it may not always be possible to know ahead of time if a sample
will be used as evidence in future legal actions, it is a good common sense
practice to institute a proper chain-of-custody in all instances. Use of such
practices as standard operating procedures on a project to project basis will
contribute to the consistency and quality of the generated data.
Sample Identification
Preprinted, preserial ized sample collection tags are recommended to
identify samples collected for shipment to the analytical laboratory.
Specific analysis tags may also be issued by the analytical laboratory after
the sample has arrived. All collected samples, including duplicates and field
blanks should be completely filled in with a minimum of the following
information:
Project Code
Assigned by the
t Location Number Document Control Officer (DCO)
Date of Co I Iect i on
T i me of Co I Iect i on
Location Description
t Signature of Sampler
D-5
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Appendix D
Revision 0
Page 6 of 11
An
i
Lab Sample Number--Assigned by the Analytical Laboratory
Remarks Section
,n example of an appropriate sample collection tag and analysis tag is shown
n Figure D-1, respectively.
After sample analysis and appropriate quality assurance checks have been
made, original sample collection tags are to be stored in a document file
maintained by the DCO and the tag serial number is recorded in a master log
for future reference. Maintaining such files and records is an important
aspect of sample traceability and provides a needed cross referencing tool
that can be used to correlate any one of the identifying numbers and sources
(e. g., collection tag, laboratory number, master log, etc.) with a specific
sample.
Chain-of-Custody Forms
There are many transfers of custody during the course of a sampling
program, from time of collection through final sample disposition, and all
samples should be accompanied by a Chain-of-Custody Record to document these
transfers. In some instances, such as in the collection of air samples on
solid sorbents, it becomes necessary to initiate custody procedures from
collection media preparation on as the sorbent itself becomes part of the
sample after collection is complete. Laboratories providing QC samples must
also initiate a custody record. The use of a customized record sheet, such as
the one shown in Figure D-2 fulfills these requirements by providing a
convenient format for recording pertinent information.
The custody records are used for a packaged lot of samples; more than one
sample will usually be recorded on one form. More than one custody record
sheet may be used for one package, if necessary. Their purpose is to document
the transfer of a group of samples traveling together; when the group of
samples changes, a new custody record is initiated. The original of the
custody record always travels with the samples; the initiator of the record
keeps the copy. When custody of the same group of samples changes hands
several times, some people will not have a copy of the custody record. This
is acceptable as long as the original custody record shows that each person
who had received custody has properly relinquished it.
In general, the following procedures should be followed when using the
custody record sheets.
t The originator fills in all requested information from the sample
tags (except in the case of air collection media and external QC
samples which will be accompanied by custody forms from the
originating faci I ity).
The person receiving custody checks the sample tag information
against the custody record. He also checks sample condition and
notes anything unusual under "Remarks" on the custody form.
D-6
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Appendix D
Revision 0
Page 7 of 11
N 1000
Ul
i
UJ
h-
O
CONTRACT NO:
PRESERVATIVE
X
UJ
9
K
UJ
a.
UJ
DESIGNATE
0
K
to
8
SampteCodo
£
K
UJ
_J
V)
SOURCE
SM Nr
ANALYSES
Volatile Or|ima
Extracttblt Or|.
Ptstieid«/PCB$
Tract Etomtnts
Cyinid*
Phsssh
Oil Mid GrMW
Solids
BOO
BKttria
Radioactivity
COO.TOC
NH3. Or|. N
Nitntt, Nitritt
Svifatt. SMrfactmts
SiiHid*
ir~. f*. Color
Pfcosplwt*
Control No.
Figure D-1 . Sample Collection Tag
D-7
-------
oo
OIM/TNM
OM/TNM
RtcmMky IfcfMtun)
REMARKS
(SifMtw*)
MM Rnwrki
OMt/Tiim
OlM/Tii
Rtciimdky (Sifiuturt)
(Si«n«tut«l
Figure 0-?. Cha1n-o^-Custody Form.
N IOOO
CD 05 T3
CO < -O
05 n>
(/) 3
00 o .a
O ^ X
-b
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Appendix D
Revision 0
Page 9 of 11
t The originator signs in the top left "Relinquished by" box and keeps
the copy.
The person receiving custody signs in the adjacent "Received by" box
and keeps the original.
The Date/Time will be the same for both signatures since custody
must be transferred to another person.
When custody is transferred to the Sample Bank or an analytical
laboratory, blank signature spaces may be left and the last
"Received by" signature box used. Another approach is to run a line
through the unused signature boxes.
In all cases, it must be readily seen that the same person receiving
custody has relinquished it to the next custodian.
If samples are left unattended or a person refuses to sign, this
must be documented and explained on the custody record.
Receipt for Samples Form
When it becomes necessary to split samples with another source, a
separate receipt for samples from (Figure D-3) is prepared and marked to
indicate with whom the samples have been split. The signature of the person
receiving the samples is required and if this person refuses to sign, it
should be noted in the "Received by" space.
This form also complies with requirements of both Section 3007(a)(2) of
RCRA and Section 104 of the Comprehensive Environmental Response Compensation
and Liability Act. These sections both state that "...If the officer,
employee or representative obtains any samples prior to leaving the premises,
he shall give to the owner, operator, or agent-in-charge a receipt describing
the samples obtained and, if requested, a portion of such sample equal in
volume or weight to the portion retained." A copy of the completed form must
be given to one of the above described individuals, even if the offer for
split samples is declined.
Custody Seals
Custody seals are narrow strips of adhesive paper used to demonstrate
that no tampering has occurred. They may be used on sampling equipment or a
house door, but they are intended for use on a sample transport container
which is not secured by a padlock. They are not intended for use on
individual sample containers.
D-9
-------
PROJ NO
PROJECT NAME
SAMPLERS iS'9"»tuni
Sphi Samples Offered
( ) Accepted ( ) Declined
STA NO
DATE
I
TIMf
*
1
u
I
SPtIT
SAMPLES
TAG NUMBERS
Neme of Facility
Facility Location
STATION DESCRIPTION
Transferred by IS'gnUurn
Dale Time
NO Of
CON
TAINERS
REMARKS
Received by iSigntmrt) Telephone
Title Date Time
Distribution Original to Coordinator Field Filet. Copy to Facility
N 349
"d TO >
en 05 -a
CQ < ~o
05 05
(/> Z!
_i Q.
00
Z! X
o
-h o o
Figure D-?. Receipt for Sample form.
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Appendix D
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Page 11 of 11
Laboratory Custody Procedures
An onsite sample bank, the sampling laboratory area and any analytical
laboratory used for analyses are considered to be working "laboratories"
subject to laboratory custody procedures. Each laboratory should have a
designated sample custodian who implements a system to maintain control of the
samples.
This includes accepting custody of arriving samples, verifying that
information on the sample tags match the Chain-of-Custody Record, assigning
unique laboratory numbers and laboratory sample tags and distributing the
samples to the analyst.
The designated custodian is also responsible for retaining all original
identifying tags, data sheets and laboratory records as part of the permanent
project file.
Questions/Problems Concerning Custody Records
If a discrepancy between sample tag numbers and custody record listings
if found, the person receiving custody should document this and properly store
the samples. The samples should not be analyzed until the problem is resolved.
The responsible person receiving custody should attempt to resolve the
problem by checking all available information (other markings on sample
container, type of sample, etc.). He should then document the situation on
the custody record and in his project logbook and notify the project QA
Manager by the fastest available means, followed by written notification.
Changes may be written in the "Remarks" section of the Custody record and
should be initialed and dated. A copy of this record should accompany the
written notification to the QA Manager.
D-11
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Appendix E
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Page 1 of 11
APPENDIX E
DECONTAMINATION PROCEDURES
Source: Interim Standard Operating Safety Guides
Revised September, 1982
Office of Emergency and Remedial Response
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Appendix E
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INTRODUCTION Pa9e 2 of 11
Personnel responding to hazardous substance incidents may become
contaminated in a number of ways, including:
t Contacting vapors, gases, mists, or particulate in the air.
t Being splashed by materials while sampling or opening containers.
Walking through puddles of liquids or on contaminated soil.
t Using contaminated instruments or equipment.
Protective clothing and respirators help prevent the wearer from becoming
contaminated or inhaling contaminants, while good work practices help reduce
contamination on protective clothing, instruments, and equipment.
Even with these safeguards, contamination may occur. Harmful materials
can be transferred into clean areas, exposing unprotected personnel. Or in
removing contaminated clothing, personnel may contact contaminants on the
clothing and/or inhale them. To prevent such occurrences, methods to reduce
contamination and decontamination procedures must be developed and implemented
before anyone enters a site and must continue (modified when necessary)
throughout site operations.
Decontamination consists of physically removing contaminants and/or
changing their chemical nature to innocuous substances. How extensive
decontamination must be depends on a number of factors, the most important
being the type of contaminants involved. The more harmful the contaminant,
the more extensive and thorough decontamination must be. Less harmful
contaminants may require less decontamination. Combining decontamination, the
correct method of doffing personnel protective equipment, and the use of site
work zones minimizes cross-contamination from protective clothing to wearer,
equipment to personnel, and one area to another. Only general guidance can be
given on methods and techniques for decontamination. The exact procedure to
use must be determined after evaluating a number of factors specific to the
incident. In addition, the decontamination procedures for sample equipment
should be developed in conjunction with the analytical lab(s).
PRELIMINARY CONCERNS
Initial Planning
The initial decontamination plan assumes all personnel and equipment
leaving the Exclusion Zone (area of potential contamination) are grossly
contaminated. A system is then set up to wash and rinse, at least once, all
the personnel protective equipment worn. This is done in combination with a
sequential doffing of equipment, starting at the first station with the most
heavily contaminated item and progressing to the last station with the least
contaminated article. Each piece of clothing or operation requires a separate
station. Figure E-1 diagrams a contamination control program showing the
layout of the contamination reduction zone.
E-2
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Appendix E
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Page 3 of 11
MCONTAMMATION
AMA
I , , .,mmm m m mmmmmm*t
EXCLUSION
ZONE
MTM
CONTAMINATION
REDUCTION
ZONE
UMNO
, HOTUM
.CONTAMINATION
CONTHOtUNt
ACCTM CONTMOC
POINT OTMANCt
ACCIMCOMTMOL
>OINT
OMMOUT *
SUPPORT
ZONE
NTIIY
ATM
Figure E-1. Contamination reduction zone layout.
E-3
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Appendix E
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Page 4 of 11
The spread of contaminants during the washing/doffing process is further
reduced by separating each decontamination station by a minimum of 3 feet.
Ideally, contamination should decrease as a person moves from one station to
another farther along the line.
While planning site operations, methods should be developed to prevent
the contamination of people and equipment. For example, using remote sampling
techniques, not opening containers by hand, bagging monitoring instruments,
using drum grapplers, watering down dusty areas, and not walking through areas
of obvious contamination will reduce the probability of becoming contaminated
which would require a less elaborate decontamination procedure.
The initial decontamination plan is based on a worst-case situation (if
no information is available about the incident). Specific conditions at the
site are then evaluated, including:
Type of contaminant.
The amount of contamination.
Levels of protection required.
t Type of protective clothing worn.
The initial system is modified, eliminating unnecessary stations or
otherwise adapting it to site conditions. For instance, the initial plan
might require a complete wash and rinse of chemical protective garments. If
disposable garments are worn, the wash/rinse step could be omitted. Wearing
disposable boot covers and gloves could eliminate washing and rinsing both
gloves and disposable boots and reduce the number of stations needed.
Contamination Reduction Corridor
An area within the Contamination Reduction Zone is designated the
Contamination Reduction Corridor (CRC). The CRC controls access into and out
of the Exclusion Zone and confines personnel decontamination activities to a
limited area. The size of the corridor depends on the number of stations in
the decontamination procedure, overall dimensions of work control zones, and
amount of space available at the site. A corridor of 75 feet by 15 feet
should be adequate for full decontamination. Whenever possible, it should be
a straight path.
The CRC boundaries should be conspicuously marked, with entry and exit
restricted. The far end is the hot line--the boundary between the Exclusion
Zone and the Contamination Reduction Zone. Personnel exiting the Exclusion
Zone must go through the CRC. Anyone in the CRC should be wearing the Level
of Protection designated for the decontamination crew. Another corridor
may be required for the entrance and exit of heavy equipment needing
decontamination. Within the CRC, distinct areas are set aside for
decontamination of personnel, portable field equipment, removed clothing,
etc. All activities within the corridor are confined to decontamination.
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Appendix E
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Personnel protective clothing, respirators, monitoring equipment,
sampling supplies, etc. are all maintained outside of the CRC. Personnel don
their protective equipment away from the CRC and enter the Exclusion Zone
through a separate access control point at the hotline.
EXTENT OF DECONTAMINATION REQUIRED
Modifications of Initial Plan
The original decontamination plan must be adapted to specific conditions
found at incidents. These conditions may require more or less personnel
decontamination than planned, depending on a number of factors.
Type of Contaminant--
The extent of personnel decontamination depends on the effects the
contaminants have on the body. Contaminants do not all exhibit the same degree
of toxicity (or other hazard). The more toxic a substance is the more extensive
or thorough decontamination must be. Whenever it is known or suspected that
personnel can become contaminated with highly toxic or skin-destructive
substances, a full decontamination procedure should be followed. If less
hazardous materials are involved, the procedure can be downgraded.
Amount of Contamination--
The amount of contamination on protective clothing is usually determined
visually. If it is badly contaminated, a thorough decontamination is
generally required. Gross material remaining on the protective clothing for
any extended period of time may degrade or permeate it. This likelihood
increases with higher air concentrations and greater amounts of liquid
contamination. Gross contamination also increases the probability of
personnel contact. Swipe tests may help determine the type and quantity of
surface contaminants.
Leve I of Protect i on--
The Level of Protection and specific pieces of clothing worn determine on
a preliminary basis the layout of the decontamination line. Each Level of
Protection incorporates different problems in decontamination and doffing of
the equipment. For example, decontamination of the harness straps and
backpack assembly of the self-contained breathing apparatus is difficult. A
butyl rubber apron worn over the harness makes decontamination easier.
Clothing variations and different Levels of Protection may require adding or
deleting stations in the original decontamination procedure.
Work Function--
The work each person does determines the potential for contact with
hazardous materials. In turn, this dictates the layout of the decontamination
line. Observers, photographers, operators of air samplers, or others in the
Exclusion Zone performing tasks that will not bring them in contact with
contaminants may not need, for example, to have their garments washed or
rinsed. Others in the Exclusion Zone with a potential for direct contact with
the hazardous material will require more thorough decontamination. Different
decontamination lines could be set up for different job functions, or certain
stations in a line could be omitted for personnel performing certain tasks.
E-5
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Appendix E
Revision 0
Page 6 of 11
Location of Contamination--
Contamination on the upper areas of protective clothing poses a greater
risk to the worker because volatile compounds may generate a hazardous
breathing concentration both for the worker and for the decontamination
personnel. There is also an increased probability of contact with skin when
doffing the upper part of clothing.
Reason for Leaving Site--
The reason for leaving the Exclusion Zone also determines the need and
extent of decontamination. A worker leaving the Exclusion Zone to pick up or
drop off tools or instruments and immediately return may not require
decontamination. However, a worker leaving to get a new air cylinder or to
change a respirator or canister may require some degree of decontamination.
Individuals departing the CRC for a break, lunch, end of day, etc., must be
thoroughly decontaminated.
Effectiveness of Decontamination
There is no method to immediately determine how effective decontamination
is in removing contaminants. Disco I orations, stains, corrosive effects, and
substances adhering to objects may indicate contaminants have not been
removed. However, observable effects only indicate surface contamination and
not permeation (absorption] into clothing. Also many contaminants are not
easi ly observed.
A method for determining effectiveness of surface decontamination is
swipe testing. Cloth or paper patches--swipes--are wiped over predetermined
surfaces of the suspect object and analyzed in a laboratory. Both the inner
and outer surfaces of protective clothing should be swipe tested. Positive
indications of both sets of swipes would indicate surface contamination has
not been removed and substances have penetrated or permeated through the
garment. Swipe tests can also be done on skin or inside clothing. Permeation
of protective garments requires laboratory analysis of a piece of the
material. Both swipe and permeation testing provide after-the-fact
information. Along with visual observations, results of these tests can help
evaluate the effectiveness of decontamination.
Equ ipment
Decontamination equipment, materials, and supplies are generally selected
based on availability. Other considerations are ease of equipment
decontamination or disposabi I ity. Most equipment and supplies can be easily
procured. For example, soft-bristle scrub brushes or long-handle brushes are
used to remove contaminants. Water in buckets or garden sprayers is used for
rinsing. Large galvanized wash tubs or stock tanks can hold wash and rinse
solutions. Children's wading pools can also be used. Large plastic garbage
cans or other similar containers lined with plastic bags store contaminated
clothing and equipment. Contaminated liquids can be stored temporarily in
metal or plastic cans or drums. Other gear includes paper or cloth towels for
drying protective clothing and equipment.
E-6
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Appendix E
Rev i s i on 0
Page 7 of 11
Decontamination Solution
Personnel protective equipment, sampling tools, and other equipment are
usually decontaminated by scrubbing with detergent-water using a soft-bristle
brush followed by rinsing with copious amounts of water. While this process
may not be fully effective in removing some contaminants (or in a few cases,
contaminants may react with water), it is a relatively safe option compared
with using a chemical decontaminating solution. Using chemicals requires that
the contaminant be identified. A decon chemical is then needed that will
change the contaminant into a less harmful substance. Especially trouble-
some are unknown substances or mixtures from a variety of known or unknown
substances. The appropriate decontamination solution must be selected in
consultation with an experienced chemist.
Establishment of Procedures
Once decontamination procedures have been established, all personnel
requiring decontamination must be given precise instructions (and practice, if
necessary). Compliance must be frequently checked. The time it takes for
decontamination must be ascertained. Personnel wearing SCBAs must leave their
work area with sufficient air to walk to CRC and go through decontamination.
CONTAMINATION DURING MEDICAL EMERGENCIES
Basic Considerations
Part of overall planning for incident response is managing medical
emergencies. The plan should provide for:
Some response team members fully trained in first aid and CPR.
Arrangements with the nearest medical facility for transportation
and treatment of injured, and for treatment of personnel suffering
from exposure to chemicals.
Consultation services with a toxicolegist.
Emergency eye washes, showers, and/or wash stations.
First aid kits, blankets, stretcher, and resuscitator.
In addition, the plan should have established methods for decontaminating
personnel with medical problems and injuries. There is the possibility that
the decontamination may aggravate or cause more serious health effects. If
prompt life-saving first aid and/or medical treatment is required,
decontamination procedures should be omitted. Whenever possible, response
personnel should accompany contaminated victims to the medical facility to
advise on matters involving decontamination.
E-7
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Appendix E
Rev i s i on 0
Page 8 of 11
Physical Iniurv
Physical injuries can range from a sprained ankle to a compound fracture,
from a minor cut to massive bleeding. Depending on the seriousness of the
injury, treatment may be given at the site by trained response personnel. For
more serious injuries, additional assistance may be required at the site or
the victim may have to be treated at a medical facility.
Life-saving care should be instituted immediately without considering
decontamination. The outside garments can be removed (depending on the
weather) if they do not cause delays, interfere with treatment, or aggravate
the problem. Respiratory masks and backpack assemblies must always be
removed. Fully encapsulating suits or chemical-resistant clothing can be cut
away. If the outer contaminated garments cannot be safely removed, the
individual should be wrapped in plastic, rubber, or blankets to help prevent
contaminating the inside of ambulances and/or medical personnel. Outside
garments are then removed at the medical facility. No attempt should be made
to wash or rinse the victim. One exception would be if it is known that the
individual has been contaminated with an extremely toxic or corrosive material
which could also cause severe injury or loss of life. For minor medical
problems or injuries, the normal decontamination procedure should be followed.
Heat Stress
Heat-related illnesses range from heat fatigue to heat stroke, the most
serious. Heat stroke requires prompt treatment to prevent irreversible damage
or death. Protective clothing may have to be cut off. Less serious forms of
heat stress require prompt attention or they may lead to a heat stroke.
Unless the victim is obviously contaminated, decontamination should be omitted
or minimized and treatment begun immediately.
Chemical Exposure
Exposure to chemicals can be divided into two categories:
Injuries from direct contact, such as acid burns or inhalation of
toxic chemicals.
t Potential injury due to gross contamination on clothing or equipment
For the contaminant inhaled treatment can only be by qualified
physicians. If the contaminant is on the skin or in the eyes, immediate
measures must be taken to counteract the substance's effect. First aid
treatment usually is flooding the affected area with water; however, for a few
chemicals, water may cause more severe problems.
When protective clothing is grossly contaminated, contaminants may be
transferred to treatment personnel or the wearer and cause injuries. Unless
severe medical problems have occurred simultaneously with splashes, the
protective clothing should be washed off as rapidly as possible and carefully
removed. _
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Appendix E
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Page 9 of 11
PROTECTION FOR DECONTAMINATION WORKERS
The Level of Protection worn by decontamination workers is determined by:
Expected or visible contamination on workers.
t Type of contaminant and associated respiratory and skin hazards.
Total vapor/gas concentrations in the CRC.
Particulate and specific inorganic or organic vapors in the CRC.
ResuIts of sw i pe tests.
t The presence (or suspected presence) of highly toxic or
skin-destructive materials.
Leve I C Use
Level C includes a full-face, canister-type air-purifying respirator,
hard hat with face shield (if splash is a problem), chemical-resistant boots
and gloves, and protective clothing. The body covering recommended is
chemical-resistant overalls with an apron, or chemical-resistant overalls and
jacket.
A face shield is recommended to protect against splashes because
respirators alone may not provide this protection. The respirator should have
a canister approved for filtering any specific known contaminants such as
ammonia, organic vapors, acid gases, and particulate.
Level B Use
In situations where site workers may be contaminated with unknowns,
highly volatile liquids, or highly toxic materials, decontamination workers
should wear Level B protection.
Level B protection includes SCBA, hard hat with face shield, chemical-
resistant gloves, and protective covering. The clothing suggested is chemical-
resistant overalls, jacket, and a rubber apron. The rubber apron protects the
SCBA harness assembly and regulatory from becoming contaminated.
DECONTAMINATION OF EQUIPMENT
Insofar as possible, measures should be taken to prevent contamination of
sampling and monitoring equipment. Sampling devices become contaminated, but
monitoring instruments, unless they are splashed, usually do not. Once
contaminated, instruments are difficult to clean without damaging them. Any
delicate instrument which cannot be decontaminated easily should be protected
while it is being used. It should be bagged, and the bag taped and secured
around the instrument. Openings are made in the bag for sampling intake.
E-9
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Appendix e
Rev i s i on 0
Page 10 of 11
Decontamination Procedures
Samp I ing Devices--
Sampling devices required special cleaning. Decontamination procedures
including solution and solvent selection must be developed in conjunction with
the designated analytical laboratory.
Tools
Wooden tools are difficult to decontaminate because they absorb
chemicals. They should be kept on site and handled only by protected workers.
At the end of the response, wooden tools should be discarded. For
decontaminating other tools, consult with the analytical laboratory and the
site safety officer.
Heavy Equ i pment
Bulldozers, trucks, backhoes, bulking chambers, and other heavy equipment
are difficult to decontaminate. The method generally used is to wash them
with water under high pressure and/or to scrub accessible parts with
detergent/water solution under pressure, if possible. In some cases, shovels,
scoops, and lifts have been sandblasted or steam cleaned. Particular care
must be given to those components in direct contact with contaminants such as
tires and scoops. Swipe tests should be utilized to measure effectiveness.
Sanitizing of Personnel Protective Equipment
Respirators, reusable protective clothing, and other personal articles
not only must be decontaminated before being reused, but also sanitized. The
inside of masks and clothing becomes soiled due to exhalation, body oils, and
perspiration. The manufacturer's instructions should be used to sanitize the
respirator mask. If practical, protective clothing should be machine washed
after a thorough decontamination; otherwise it must be cleaned by hand.
Persistent Contamination
In some instances, clothing and equipment will become contaminated with
substances that cannot be removed by normal decontamination procedures. A
solvent may be used to remove such contamination from equipment if it does not
destroy or degrade the protective material. If persistent contamination is
expected, disposable garments should be used. Testing for persistent
contamination of protective clothing and appropriate decontamination must be
done by qualified laboratory personnel.
Disposal of Contaminated Materials
All materials and equipment used for decontamination must be disposed of
properly. Clothing, tools, buckets, brushes, and all other equipment that is
contaminated must be secured in drums or other containers and labeled.
Clothing not completely decontaminated onsite should be secured in plastic
bags before being removed from the site.
E-10
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Appendix E
Rev i s i on 0
Page 11 of 11
Contaminated wash and rinse solutions should be contained by using
step-in-containers (for example, child's wading pool) to hold spent
solutions. Another containment method is to dig a trench about 4 inches deep
and line it with plastic. In both cases the spent solutions are transferred
to drums, which are labeled and disposed of with other substances onsite.
E-11
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Appendix F
Revision 0
Page 1 of 7
APPENDIX F
INSTRUMENT CERTIFICATM
Source: "Hazardous Materials Incident Response Operations'
Training Course Manual (165.1)
F-1
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Appendix F
Revision 0
Page 2 of 7
INHERENT SAFETY
The portable instrumentation used to evaluate hazardous material spills
or waste sites must be demonstrated as being safe to use in those hostile
environments. Electrical devices, such as the monitoring instruments, must be
constructed in such a fashion as to eliminate the possibility of igniting a
combustible atmosphere. The sources of this ignition could be an arc generated
by the power source itself or the associated electronics, and/or a flame or
heat source inherent in the instrument and necessary for its proper functioning.
Several engineering, insurance, and safety industries have standardized
test methods, established inclusive definitions, and developed codes for
testing electrical devices used in hazardous locations. The National Fire
Protection Association (NFPA), a forerunner in this endeavor, has created
minimum standards in its National Electrical Code (NEC), which is published
every 3 years.
This code spells out, among other things, the following:
Types of controls acceptable for use in hazardous atmospheres.
Types of areas in which hazardous atmospheres can be generated and
the types of materials that generate these atmospheres.
HAZARDOUS ATMOSPHERES
Depending upon the response worker's background, the term "hazardous
atmosphere" conjures up situations ranging from toxic air contaminants to
flammable atmospheres. For our purposes, an atmosphere is hazardous if it
meets the following criteria:
It is a mixture of any flammable material in air (see Class and
Group below) whose composition is within this material's flammable
range (LEL-LFL).
A critical volume of the mixture is sufficiently heated by an
outside ignition source.
The resulting exothermic reaction propagates the flame beyond where
it started.
Hazardous atmospheres can be produced by one of three general types of
materials:
Flammable gases/vapors
Combustible dusts
t Ignitable fibers
F-2
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Appendix F
Revision 0
Page 3 of 7
Whereas the flammable material may define the hazard associated with a
given product, the occurrence of release (how often the material generates a
hazardous atmosphere) dictates the risk. Two types of releases are associated
with hazardous atmospheres:
Continuous: Those existing continuously in an open unconfined area
during normal operating conditions.
Confined: Those existing in closed containers, systems, or piping,
where only ruptures, leaks, or other failures result in a hazardous
atmosphere outside the closed system.
There are six possible environments in which a hazardous atmosphere can
be generated. However, not every type of control will prevent an ignition in
every environment. To adequately describe the characteristics of those
environments and what controls can be used, the National Electrical Code
defines each characteristic:
Class is a category describing the type of flammable material that
produces the hazardous atmosphere:
Class I is flammable vapors and gases, such as gasoline, and
hydrogen. Class I is further divided into groups A, B, C, and D on
the basis of similar flammability characteristics (Table F-1).
Class II consists of combustible dusts like coal or grain and is
divided into groups E, F, and G.
Class III is ignitable fibers such as produced by cotton milling.
Division is the term describing the "location" of generation and release
of the flammable material.
Divisionl is a location where the generation and release are
continuous, intermittent, or periodic into an open, unconfined area
under normal conditions.
Division 2 is a location where the generation and release are in
closed systems or containers and only from ruptures, leaks, or other
fai lures.
Using this system, a hazardous atmosphere can be routinely and adequately
defined. As an example, a spray-painting operation using acetone carrier
would be classified as a Class I, Division 1, Group D environment.
Additionally, an abandoned waste site containing intact closed drums of methyl
ethyl ketone, toluene, and xylene would be considered a Class I, Division 2,
Group D environment. Once the containers begin to leak and produce a hazardous
atmosphere, the environment changes to Class I, Division 1, Group D.
F-3
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Appendix F
Rev i s i on 0
Page 4 of 7
TABLE F-1. CLASS I CHEMICALS BY GROUP
Group A Atmospheres
Acetylene
Group B Atmospheres
Acrolein (inhibited)
Arsine
Ethylene oxide
Hydrogen
Manufactured gases containing more
than 30% hydrogen (by volume)
Propylene oxide
Propylnitrate
Group C Atmospheres
Acetaldehyde
Allyl alcohol
n-Butyraldehyde
Carbon monoxide
Cyclopropane
Diethyl ether
Diethylamfne
Epichlorohydrin
Ethylene
Ethyleneimine
Ethyl mercaptan
Ethyl sulfide
Hydrogen cyanide
Hydrogen sulfide
Morphol i ne
2-Nitropropane
Tetrahydrofuran
Unsynmetrical dimethyl hydrazine
(UDMH, 1-, 1-dimethyl hydrazine)
(butyl alcohol)
(secondary butyl alcohol)
Group D Atmospheres
Acetic Acid (glacial)
Acetone
Acrylonitri le
Ammon i a
Benzene
Butane
1-Butanol
2-Butanol
n- Butyl acetate
Isobutyl acetate
di - Isobutylene
Ethane
Ethanol (ethyl alcohol)
Ethyl acetate
Ethyl aery I ate (inhibited)
Ethyl diamine
Ethylene di chloride
Ethylene glycol monomethyl ether
Gasol ine
Heptanes
Hexanes
Isoprene
Isopropyl ether
Mesityl oxide
Methane (natural
Methanol (methyl
3-Methyl -1-butanol (isoamyl alcohol)
Methyl ethyl ketone
Methyl isobutyl ketone
2-Methyl -1-propanol (isobutyl
2-Methyl -2-propanol
Octanes
naphtha3
gas)
alcohol)
alcohol)
(tertiary butyl alcohol)
Petro I eum
Pentanes
1-Pentanol
Propane
1-Propanol
2-Propanol
Propylene
Pyridine
Styrene
Toluene
Vinyl acetate
Vinyl chloride
Xy lenes
(amyl alcohol)
(propyl alcohol)
(isopropyl alcohol]
A saturated hydrocarbon mixture boiling in the range 20° - 135°C ((
known by the synonyms benzine, ligroin, petroleum ether, or naphtha.
'- 275°F). Also
Source: National Electrical Code. Vol. 70, Table 500-2. National Fire Protection
Association, 470 Atlantic Avenue, Boston, MA 02210 (1981).
F-4
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Appendix F
Revision 0
Page 5 of 7
CONTROLS
Three methods exist to prevent a potential ignition source from igniting a
flammable atmosphere:
t Explosion-proof: Encase the ignition source in a rigidly built
container. "Explosion-proof" instruments allow the flammable
atmosphere to enter. If and when an arc is generated, the ensuing
explosion is contained within the specially designed and built
enclosure. Within it, any flames or hot gases are cooled prior to
exiting into the ambient flammable atmosphere so that the explosion
does not spread into the environment.
Intrinsically Safe: Reduce the potential for arcing among
components by encasing them in a solid insulating material. Also,
reducing the instrument's operational current and voltage below the
energy level necessary for ignition of the flammable atmosphere
provides equal protection. An "intrinsically safe" device, as
defined by the National Electrical Code, is incapable "of releasing
sufficient electrical or thermal energy under normal or abnormal
conditions to cause ignition of a specific hazardous atmospheric
mixture in its most easily ignited concentration. Abnormal
conditions shall include accidental damage to any ... wiring,
failure of electrical components, application of over-voltage,
adjustment and maintenance operations and other similar conditions."
Purged: Buffer the arcing or flame-producing device from the
flammable atmosphere with an inert gas. In a pressurized or
"purged" system, a steady stream of, for example, nitrogen or helium
is passed by the potential arcing device, keeping the flammable
atmosphere from the ignition source. This type of control, however,
does not satisfactorily control analytical devices that use a flame
or heat for analysis such as a combustible gas indicator (CGI) or
gas chromatography (GC).
CERT IFI CAT I ON
National groups such as Underwriters Laboratories (UL), Factory Mutual
(FM), and the American National Standards Institute (ANSI), together with NFPA,
have developed test protocols for certifying explosion-proof, intrinsically
safe, or purged devices to meet minimum standards of acceptance.
An electrical device certified under one of these test methods carries a
permanently affixed plate showing the logo of the laboratory granting
certification and the Class(es), Division(s), and Group(s) it was tested
against. See Figure F-1.
F-5
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Appendix F
Revision 0
Page 6 of 7
AA5A
Combustible Gas and 0* Alarm
UCTMTMTUM
model 260 part no. 449900
calibnud fof| Pentane
intrlniJctlhr S*f« tor VM IA Murdov* Ivciliont Cl«tl I. Division 1.
Groups C «nd D (nd Nen-lnccrtdlv* for «M In Otu 1. OMsion 2. Croupt A.
B, C. »nd 0 irhtn wt*d «ritH MSA Battery. f*t Ne. 4S7M9.
MUST BE OPERATED IN ACCORDANCE WITH INSTRUCTIONS
MFD. BY
MNE SAFETY APPLIANCES COMPANY
PITTSBURGH PCNNSVUAMA. US. A. 1S20S
ntn *n t «.«. MT. M. J.MUM Mnmt M CAMM «»
Figure F-1. Example Device Certification Plate
Certification means that if a device is certified as explosion-proof,
intrinsically safe, or purged for a given Class, Division, and Group, and is
used, maintained, and serviced according to the manufacturer's instructions,
it will not contribute to ignition. The device is not, however, certified for
use in atmospheres other than those indicated.
Any manufacturer wishing to have an electrical device certified by FM or
UL must submit a prototype for testing. If the unit passes, it is certified
as submitted. However, the manufacturer agrees to allow the testing
laboratory to randomly check the manufacturing plant at any time, as well as
any marketed units. Furthermore, any change in the unit requires the
manufacturer to notify the test laboratory, which can continue the
certification or withdraw it until the modified unit can be retested.
A unit may be certified either by UL, FM, or
ow test protocols establ ished by NFPA and ANS
fo
certification
consideration
and Group(s)
both. Both Laboratories
. Therefore one
is no better or worse than the other. The important
is that the device is approved for the Class(es), Division(s),
it wi I I be used in.
The mention of FM or UL
not guarantee certification.
(flammable) locations must be
NEC Table 500-2(b).
in the manufacturer's equipment literature does
All certified devices that are used in hazardous
marked to show Class, Division, and Group, per
Other organizations such as the Mine Safety and Health Administration
(MSHA), Canadian Standards Association (CSA), National Electrical
Manufacturers Association (NEMA), and the U.S. Coast Guard (USCG) have
developed their own testing and certification schemes for electrical devices
in hazardous locations common to their jurisdiction.
F-6
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Appendix F
Rev i s i on 0
Page 7 of 7
MSHA tests and certifies electrical equipment to be used in hazardous
atmospheres associated with underground mining. These atmospheres usually
contain methane gas and coal dust; hence, the tests and certification are
specific to those two contaminants.
Often the same monitoring equipment is used both in mines and above ground
and would carry more than one certification, such as FM and MSHA.
To ensure personnel safety, it is recommended that only approved (FM or
UL) instruments be used onsite and only in atmospheres for which they have
been certified. When investigating incidents involving unknown hazards, the
monitoring instruments should be rated for use in the most hazardous
locations. The following points will assist in selection of equipment that
will not contribute to ignition of a hazardous atmosphere:
In an area desigated Division 1, there is a greater probability of
generating a hazardous atmosphere than in Division 2. Therefore,
the test protocols for Division 1 certification are more stringent
than those for Division 2. Thus, a device approved for Division 1
is also permitted for use in Division 2, but not vice versa. For
most response work this means that devices approved for Class I
(vapors, gases), Division 1 (areas of ignitable concentrations),
Groups A, B, C, D should be chosen whenever possible. At a minimum,
an instrument should be approved for use in Division 2 locations.
All instruments to be used in a methane environment should be
approved by the Mine Safety and Health Administration (MSHA) as being
safe in such atmospheres.
There are so many Groups, Classes, and Divisions that it is impossible
to certify an all-inclusive instrument. Therefore, select a certified
device based on the chemicals and conditions most likely to be en-
countered. For example, a device certified for a Class II, Division
1, Group E (combustible metal dust) would offer little protection
around a flammable vapor or gas.
F-7
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Appendix G
Revision 0
Page 1 of 4
APPENDIX G
APPLICABLE TABLES
G-1
-------
TABLE G-1.
03
97
16
12
55
16
84
63
33
57
18
26
23
52
37
70
56
99
16
31
47
74
76
56
59
22
42
01
21
60
18
62
42
36
85
29
62
49
08
16
43
24
62
85
56
77
17
63
12
86
07
38
40
28
94
17
18
57
15
93
73
67
27
99
35
94
53
78
34
32
92
97
64
19
35
12
37
22
04
32
86
62
66
26
64
39
31
59
29
44
46
75
74
95
12
13
35
77
72
43
36
42
56
96
38
49
57
16
78
09
44
84
82
50
83
40
96
88
33
50
96
81
50
96
54
54
24
95
64
47
17
16
97
92
39
33
83
42
27
27
RANDOM NUMBERS
47
14
26
68
82
43
55
55
56
27
16
07
77
26
50
20
50
95
14
89
36
57
71
27
46
54
06
67
07
96
58
44
77
11
08
38
87
45
34
87
61
20
07
31
22
82
88
19
82
54
09
99
81
97
30
26
75
72
09
19
46
42
32
05
31
17
77
98
52
49
79
83
07
00
42
13
97
16
45
20
Appendix G
Rev i s i on 0
Page 2 of 4
98
53
90
03
62
37
04
10
42
17
83
11
45
56
34
89
12
64
59
15
63
32
79
72
43
93
74
50
07
46
86
46
32
76
07
51
25
36
34
37
71
37
78
93
09
23
47
71
44
09
19
32
14
31
96
03
93
16
68
00
62
32
53
15
90
78
67
75
38
62
62
24
08
38
88
74
47
00
49
49
INSTRUCTIONS FOR THE USE OF THE RANDOM NUMBER TABLE
1. Number the members of the lot (i.e., the drums onsite, the sections
within a grid) in a numerical order.
2, Decide on the number of samples necessary. This should be a number
sufficient to give statistical significant data. Ten to 20 percent
is usually adequate. This number should be predetermined in the test
plan or should coincide with the time and equipment available.
3, Using the set of random numbers above; choose any number as a starting
point, then proceed to select the next number in any predetermined
direction (i.e., down the column, across the rows) until the selection
process has yielded the desired number of samples.
G-2
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Appendix G
Revision 0
Page 3 of 4
TABLE G-2. CONVERSI
FACTORS/TABLES OF MEASUREMENT
Length and awM
i toe: <* -UMMa
- 30.48 (
1 art (to.) - 19.491
199 ft per a* - 9.908 eMtor per etc
0"4
fW
-9.9929 Hi
-8,45 HI
- MOOMStors
- 0.921 sMuto m8e
i (cm)
- 1.094 M*
-3J911eet
- 38.37 Mws
- 11 tt» assume (A-)
0.001 mMmetor
'U8 Mirttoa
1kg per cum
llpereum
2240 pounds
1010 ttograms
907Mognm
7000 grains
0.454 Mogram
0.0025 oound
28.35 grams
'gram per Her
I p*l *er 9wusand
Img per tiler
1 tart per mMon
. - 8.33ftpermMonga<
* 143 ft per mikon go
I - 0.12ppm
IftpermMor.caf - 0.007 gran per gafen
-790 mm (29.92 in.)
ejtorcury Mft density
O.S95 gamj s« cc
MISCELLANEOUS
- 84.8mHgnms
- 0.0023 ounce
- 1.488 kg per meter
- lOOOklograms
- 0.984 tang ton
- 1.102 U.S. short tons
-2205 pounds
- 1000 grams
- 2.205 pounds
- 1000 milgrarns (mg)
- 0.03527 ounce
- 15.43 gram
- 0.672 pound per ft
- 27euft
- 0.765 cu m
- 1728 cu in.
- 28.32 Men
-7.48U.S.
- 16.39 cn centi-
meters (cu cm)
- 277.4 cu to.
1 pound per toot
1 metric ton
(MM)
(kg)
1gnm(g)
1 kg par mtor
Volumo
1 cubic toot
1 knp«M gtfon
1 U.S. geNon - 0.833 Imperial
1 US. barrel
(petrotouT.)
1 cubic meter
(cum)
Ittar
3.7
231cuin.
0.1337 cuff
42 U.S. gelkm
35 Imperial gaUons
1000 Men
35.31 cu ft
1000 cc
0.2200 imp***
gallon
0 2642 U.S. 0*)lon
61.Oca in.
14.696 R> per sq in.
1.033kg per sq cm
t kg per sq cm
10.000 kg per sq m
- 10 m head of Mfcr
- 14.22 ft per sq in.
IK, per squire foot- 0.1924 in of wetor
- 4.88 kg pet sq m
2.036 in head of
mercury
2.309 ft hoed of
1 ttnocphere
-(metric)
it> per squirt
Hch
1 ton per squirt
ktch
tktchNatfol
- 0.0703 kg per sq cm
- 0.0690, tar
- t.408 kg per sq mm
- $.20 ft per sq ft
lloertfool -ttkt.x12ki.i1li.
let ft pern* - 1.999 cum par haur
1 cum per haw - 0.599 cu ft per mki
1 gjlon per mki - 0.00144
MrMy
Etonafty (wi
tcuftperft
Iftpircuft
1 grain per curl
1 grain per U.S.
9J824cunasri9
18 02 kg 17
praim
17.11
17.11
18.02 aft per ft
0.0824 ft par aft
0.437 gmki per cu ft
0.0894 grata per U.S.
1 cu m per kg
1 kg per cum
1 gnmpercum
t gram per cc
i gram per Mcr
Watar at 92 F (19,7 Q
1 cubic toot -923ft
1 pound - 9.91904 cu ft
1U.S.
92 4 ft pare* ft
N.4fMlMI*rw.S.
Watar at 39 J F (4 Q,
maomum dmsfty
1 cubic toot -92.4ft
tomcmetor - WOO kg
1 pound - 0.01902 cu ft
1Kor - 1.0kg
1 toot need of - 0.433 ft per * »
- 0.1 kg par sq on
- 0.491 ftperaqn
- 1.390 kg per sq on
- 1mm Mad of MCI
> 9.2048 ft per sqtt
735.5 mm ef mtrcun
14.22 ft per SB. *
0.711 ton per aq m
1 m hod of water
1 h. head of
mercury
imheedof
mercury
1 Mtognm per eq
m
1 Uogramparaq
cm
1 kg par aq mm
to SMSO caavertiaM. toeaas aad Htt of
M 82 f (18.7 0. *!
M3I.2FHO.
Jew-
Source : Betz Handbook of Industrial Water Conditioning, 1976
seventh edition, Betz Laboratories, Inc., Trevose, PA
G-3
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Appendix G
Rev i s i on 0
Page 4 of 4
ExampIe:
Soil samples are to be collected from a field 10 meters by 15 meters in
area. Equipment and laboratory arrangements have been made to handle eight
samples.
A. The area is divided into an imaginary 1 meter grid.
B, Each quadrant in the grid is assigned a number in a numerical
order; West to East, North to South (or left to right, top to
bottom).
c, Referring to the Random Number table it is arbitrarily decided to
start at the first number in the third row, then proceed down the
column.
This would result in the selection of 43 as the first number followed
by 24, 62, 85, 56, 77, 17 and 63 as the eighth and final selection.
The grids corresponding to these numbers would then be sampled.
Q _ A -.-US GOVERNMENT PRINTING OFFICE 1985- 559- 111/10754
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