PB88-173364
Sampling and Analysis of
Hazardous Wastes
(O.S.) Environmental Monitoring Systems Lab.
Research Triangle Park, NC
Feb 88
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EPA/600/D-88/035
February 1938
SAMPLING AND ANALYSIS OF HAZARDOUS WASTES
By
Larry D. Johnson
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
Ruby H. James
Southern Research Institute
Brimingharo, AL
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OH 45268
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TECHNICAL REPORT DATA
(Plette rtud liHtmeliom on the ftitnr be fort fomfteimfi
1. REPORT NO. "2.
4. TITLE AND SUBTITLE
Sampling and Analysis of Hazardous Wastes
7. AVITHORIS)
Larry D. Johnson and Ruby H. James
9. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. EPA, EMSL, Research Triangle Park, NC
Southern Research Institute, Birmingham, AL
ana
12. SPC.4SORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
EMSL-RTP/QAD/Source Branch (MD-77A)
Research Triangle Park, NC 27711
3 "UCi'ltNT-S ACCESSION NO.
S. REPORT DATE
February 1988
B. PERFORMING ORGANIZATION CODE
B. PERFORMING ORGANIZATION REPORT
NO.
10. PROGRAM ELEMENT NO.
11. CONTRACT /GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-600/08
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
This chapter is a relatively brief overview and guide to the very complicated
endeavor of sampling and analysis of hazardous waste and related products. Stack
sampling and analysis of waste combustion products is emphasized partly due to the
authors' backgrounds and partly due to the relatively recent development of most of
the technology.
17. KF.V WORDS AND DOCUMENT ANALYSIS
1. DESCRIPTORS
Stack sampling
Waste sampling
Waste analysis
Waste combustion
Organic analysis
18. DISTRIBUTION STATEMENT
b. IDENTIFIERS/OPEN ENOED TERMS C. COS AT 1 Field 'Croup
19. SECURITY CLASS (Thii Krpart! 21. NO. Of PAGES
Unclassified / B 3
2O. SECURITY CLASS iTWlffgtl 22. PRICE
Unelassifipd fl ft t /?. 9<5
EPA POT* 2720.1 (••*. 4-77) PDCVIOU* COITION •• OBSOLETE
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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8. Sampling and Analysis of Hazardous Wastes
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CHAPTER 8
SAMPLING AND ANALYSIS OF HAZARDOUS WASTES
Larry D. Johnson
U. S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
Ruby H. James
Southern Research Institute
8.1 INTRODUCTION
8.2 SAMPLING OF HAZARDOUS WASTE AND RELATED PRODUCTS
8.2.1 Sampling Hazardous Waste
3.2.2 Sampling Waste Combustion Products
8.2.3 Sampling Solid and Liquid Effluents from
Combustion and Control Devices
8.2.4 Sample Containers, Shipping and Storage
8.2.5 Quality Control and Quality Assurance
8.2.6 Safety
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8.3 ANALYSIS OF HAZARDOUS WASTE AND RELATED PRODUCTS
8.3.1 Background
8.3.2 Analytical Methods
8.3.3 Considerations Associated with Hazardous Wasti
Analysis
8.3.4 Analysis of Hazardous Waste
8.3.5 Analysis of Hazardous Waste Combustion Products
8.3.6 Use of Surrogates
8.3.7 Documentation
8.3.8 Quality Assurance/Quality Control
8.3.9 Conclusions
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8.1 INTRODUCTION
Early attempts to cope with environmental pollution problems
generally dealt with one or two specific substances. Flue gas
emissions were primarily studied and regulated by the classical
SOX, NOX, and "particulate" approach. As awareness of poten-
tially harmful effects of more and more materials grew, research
studies began to characterize larger numbers of pollutants from a
variety of sources. This effort required development of sampling
and analysis methods with broader scope and the ability Co produce
information as cost-effectively as possible (1-3). Cue of the
first regulatory programs to deal with increased numbers of
pollutants was the EPA Effluent Guideline Program, for which new
sampling and analysis procedures were developed and validated
(4-6).
Today, regulators, the regulated community, and researchers
alike are still adjusting their approaches and procedures for
de&ling with hazardous waste problems, caused by hundreds of
different compounds in solid, liquid, gaseous, or mixed media.
Major programs to develop and validate sampling and analysis
methods have been started And are still under way. Many of the
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methods are still stcte-of-the-art technology, and their applica-
tion requires considerable expertise. The sampling programs and
the subsequent analysis efforts are often complex, difficult, and
expensive. Success depends on careful planning and execution, as
well as thorough knowledge of the field. This chapter is a rela-
tively brief overview and guide to the very complicated endeavor
of sampling and analysis of hazardous waste and related products.
The references have been selected because of their general useful-
ness and because they can guide the interested reader to more
detailed literature.
8.2 SAMPLING OF HAZARDOUS WASTE AND RELATED PRODUCTS
Sampling of hazardous waste includes a number of diverse
activities. It may be necessary to sample waste contained in
tanks or drums, in ponds, in piles, or from various processing or
transporting equipment such as conveyor belts. In addition, it
may be necessary to sample waste that has been diluted or trans-
formed by leaching, spills, or various forms of treatment
technology.
Two of the major tasks related to sampling of wastes in any
form are planning the sampling strategy and selecting the detailed
tactics necessary for support of the strategy. The sampling
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strategy must be consistent with the goals of the overall project,
and must include selection of major waste impoundments, con-
tainers, or streams to be characterized. In addition, the proper
degree of sampling resolution must be determined. For example,
one might choose to characterize liquid in & waste storage tank,
flue gas from an incinerator stack, and water in a scrubber efflu-
ent holding pond. One must then decide whether an average value
is sufficient for each component of interest in each of these
wastes, or whether more detail is needed. Detailed characteriza-
tion of the materials within each of these units might include the
homogeneity of their distribution or the spatial variation of
distribution within the unit.
Once the sampling strategy has been developed, detailed
factics can be planned. This planning of tactics includes
decisions concerning the number of replicate samples to be taken,
whether to combine samples into composites or analyze separately,
selection of sampling methods or hardware, selection of sample,
packing and shipping methods, and many other seemingly innocuous
details. In truth, each of these details may be critical to the
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success of the progran goal and must be given careful thought
and consideration.
8.2.1 Sampling Hazardous Waste
The few basic references in this field invariably point out
that hazardous wastes may be complex, multiphase mixtures that
have a great variety of physical and chemical properties. As
mentioned earlier, the waste itself may be contained in a wide
variety of vessels or in ponds or spread throughout sizeable areas
of soil. Because of all these possibilities, one standard
protocol for sampling hazardous waste cannot be formulated. Each
project will require considerable planning and tailoring of the
sampling approach to meet the overall objectives.
The strategies and tactics of planning and carrying out the
sampling are a great deal more complex than the equipment with
which the samples are usually taken. The equipment itself is
usually exceptionally simple and inexpensive, especially when
compared with the stack-sampling hardware discussed in
Section 8.2.2.
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Sampling Waste Conbi-ftion Products
The methods of selecting the sampling grid, the number of
replicates needed, and the expected results in terras of precision
and accuracy draw heavily on statistics and cannot be discussed
fully in this general overview. The traditional sampling proce-
dures include: simple random, stratified random, systematic ran-
dom, authoritative, and composite. In simple random sampling, all
locations in the batch of waste are identified, and a suitable
number of these are randomly selected for sampling. Stratified
random sampling is used when the waste is known to be randomly
heterogeneous; in this case, the population of locations is strat-
ified to isolate che source of nonrandom distribution, and each
stratum may be sampled by simple random sampling. In systematic
random sampling, the first unit is sampled randomly, and all other
units are selected at fixed intervals from the first: these
intervals may be spatial or time intervals. In authoritative
sampling, based on an individual's thorough knowledge of the
waste, samples are selected according to the known distribution of
chemical impurities and are tailored to be consistent with the
overall sampling strategy; this procedure is very seldom recom-
mended for hazardous waste, and almost never in a regulatory
si. tuition.
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When little is known about the distribution of chemical
pollutants in the waste, simple random sampling is usually the
best choice (7). As one gains more information about Che distri-
bution, it may become possible to employ stratified random sam-
pling, systematic random sampling, or even authoritative sampling.
For certain applications such as plume definition, geostatistical
sampling appears to be a very promising technique (8). The waste
sampling references (7-11) contain more detailed discussion of
the procedures involved.
Table 8.1 provides examples of sampling equipment commonly
u.ied in sampling waste in various containers or impoundments.
The following illustration and short descriptions of waste
sampling equipment (transferred from reference 7) demonstrate the
nature and uses of some of the more common hardware employed.
Composite Liquid Waste Sampler
The composite liquid waste sampler, or Coliwasa (Figure 8.1),
is a device employed to sample free-flowing liquids and slurries
contained in drms, shallow tanks, pits, and similar containers.
It is especially useful for sampling wastes thac consist of
several immiscible liquid phases. The Coliwasa consists of *
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glass, plastic, or metal tube equipped with an end closure that
can be opened and closed while the tube is submerged in the
material to be sampled.
Weighted Bottle
The sampler consists of a glass or plastic bottle, sinker,
stopper, and a line that is used to lower, raise, and open the
bottle (Figure 8.2). The weighted bottle samples liquids and
free-flowing slurries. A weighted bottle with line is built to
the specifications in ASTN Methods D270 and E300.
Dipper
The dipper (Figure 8.3) consists of a glass or plastic beaker
clamped to the end of a two- or three-piece telescoping aluminum
or fiberglass pole that serves as the handle. A dipper samples
liquids and free-flowing slurries. Dippers are not available
commercially and must be fabricated.
Thief
A thief (Figure 8.4) consists of two slotted concentric
tubes, usually made of stainless steel or brass. The outer tube
has a conical pointed tip that permits the sampler to penetrate
the material being sampled. The inner tube is rotated to open and
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close the sampler. A thief is used to sample dry granules or
powdered wastes whose particle diameter is less than one-third
the width of the slots. A thief is available at laboratory supply
stores.
Trier
A trier (Figure 8.S) consists of a tube cut in half length-
wise with a sharpened tip that allows the sampler to cut into
sticky solids and to loosen soil. A trier samples moist or sticky
solids with a particle diameter less than one-half the diameter of
the trier. Triers 61 to 100 cm long and 1.27 to 2.54 cm in
diameter are available at laboratory supply stores. A large trier
can be fabricated.
Auger
An auger consists of sharpened spiral blades attached to a
hard-metal central shaft. An auger samples hard or packed solid
wastes or soil. Augers are available at hardware and laboratory
supply stores.
Scoops and Shovels
Scoops and shovels are used to sample granular or powdered
material in bins, shallow containers, and conveyor belts.
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Scoops are available at laboratory supply houses. Flat-nosed
shovels are available at hardware stores.
Bailer
The bailer is employed for sampling well water. It consists
of a container attached to a cable that is lowered into the well
to retrieve a sample. Bailers can be of various designs. The
simplest is a weighted bottle or basally capped length of pipe
that fills from the top as it is lowered into the well. Some
bailers have a check valve, located at the bade, which allows
water to enter from the bottom as the device is lowered into the
well. When the bailer is lifted, the check valve closes, allowing
water in the bailer to be brought to the surface. Mere sophisti-
cated bailers are available that remain open at both enda while
being lowered, but can be sealed at both top and bottom by acti-
vating a triggering mechanism from the surface. This allows more
reliable sampling at discrete depths within a well. Perhaps the
best-known bailer of this latter design is the Kemmerer
sampler.
Bailers generally provide an excellent means for collecting
samples from monitored wells. They can be constructed from a
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wide variety of materials compatible with the parameter of
interest. Because they are relatively inexpensive, bailers can
be easily dedicated to an individual well to minimize cross-
contamination during sampling. If not dedicated to a well, they
can be easily cleaned to prevent cross-contamination. Unfortun-
ately, bailers are frequently not suited for well evacuation
because of their small volume.
Suction Pumps
As the name implies, suction pumps operate by creating a
partial vacuum in a sampling tube. This vacuum allows the
pressure exerted by the atmosphere on the water in the well to
force water up the tube to the surface. Accordingly, these pumps
are located at the surface and require only that a transmission
tube be lowered into the well. Unfortunately, their use is
limited by their reliance on suction to depths of 20 to 25 ft,
depending on the pump. In addition, their use may result in
outgassing of dissolved gases or volatile organics and is there-
fore limited in many sampling applications. In spite of this,
suction methods may provide a suitable means for well evacuation
because the water remaining in the well is left reasonably
undisturbed.
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Positive Displacement Pumps
A variety of positive displacement pumps is available for use
in withdrawing water from wells. These methods use a pumping
mechanism placed in the well that forces water from the bottom of
the well to the surface by some means of positive displacement.
This minimizes the potential for aerating or stripping volatile
organics from the sample during removal from the well.
Further details are available about pumps (7^) as well as
about vacuum extractors, pressure-vacuum lysimeters, and trench
lysimeters. The latter three types of devices may be useful for
sampling surface water and groundwater.
DeWee, et al. Ill)* indicate that brushes and vacuum cleaners
are useful when sampling dust from hard surfaces.
It is not particularly desirable, and probably not even
possible, to list all possible tools or devices that may be used
for sampling hazardous waste. As stated earlier, the various
hazardous wastes may exhibit a great diversity of properties and
may be contained in a wide variety of vessels or impoundments.
Performing the sampling properly may call for ingenuity as well
as knowledge.
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8.2.2 Sampling Waste Combustion Products
The increasing importance of combustion as a disposal tech-
nique for hazardous waste has resulted in considerable interest
in methods for sampling flue gas emissions. Waste may also be
destroyed by cofiring it in industrial boilers or other units such
as lime kilns.
Sampling equipment for flue gases is usually more complicated
than that used for waste itself, or even for soil and groundwater.
This is because the flue gas consists of a multiphase system and
is usually at an elevated temperature. Because any of the phases
may contain emissions of interest, and many of the combustion
products interfere with collection of others, the flue gas must be
subjected to filtration, cooling, and various forms of solvent
scrubbing or sorption to solid substrates. Measuring gas volumes
sampled is thus inherently more difficult and cumbersome than
measuring liquid or solid sample volumes or weights.
Of the many sampling devices used over the years, only a few
are discussed here. These pieces of equipment are widely used,
versatile, and commercially available, and their performances are
reasonably well known for the more common pollutants. Readers
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interested in more specialized or more exotic sampling approaches
can easily locate them in the literature with the aid of the
general references given at the end of this chapter.
To ensure that a representative sample is obtained, the
sampling probe is usually moved from place to place in the stack
according to a prearranged plan. EPA Method 1 (12) gives details
on designing the sampling pattern. This practice is called
traversing the stack and compensates for stratification of
material in the stack.
Another important concept is that of isokinetic sampling. If
the velocity of the sample gas drawn into the probe is closely
matched to that passing past the probe, the sampling is said to
be isokinetic. A mismatch in these velocities results in aniso-
kinetic sampling. Inertial effects during anisokinetic sampling
may result in overcollection or undercollection of particulate
matter, depending upon its size and mass. This effect does not
occur for gases and is generally of marginal importance for
particulate material less than 2 ura in diameter
The Source Assessment Sampling System (SASS), Figure 8.6, was
developed for environmental assessment programs and is still the
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train of choice when large amounts of samples are necessary for
extended chemical analysis or biotesting. The SASS includes
cyclones for particle sizing, a glass or quartz fiber filter for
fine particle collection, a scrbent module for collection of
semivolatile organics, and impingers for collection of volatile
metals. The SASS operates at 110 to 140 L/min (4 to 5 ft3'min)
and is usually operated long enough to collect 30 m? of flue
gas.
The large size of the SASS makes traversing inconvenient but
not impossible unless precluded by physical arrangements at the
sampling site. The particle-sizing cyclones require consistent
gas flow (monitored with a pitot tube and manometer) through th
for proper operation, which limits flow adjustments necessary for
true isokinetic sampling. The SASS has been operated, without the
cyclones, in the full traverse and isokinetic sampling mode, but
the Difficulty of this option makes it unattractive. It is
usually operated at a single point in the stack under pseudo-
isokinetic conditions. Under most circumstances, this mode of
operation results in samples that are indistinguishable from those
taken under true isokinetic conditions. Because results may be
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less quantitative or representative samples taken in this manner
are somewhat less defensible. Further details on this subject are
available (n, _14) .
Potential corrosion of stainless steel in the sorbeot module
of the SASS has prompted development of glass sorbent modules,
which appear to perform adequately. The glass sorbent module, as
well as detailed information concerning construction and operation
of both the SASS and the Modified Method Five (MHS) trains is
described elsewhere (]_, 15).
The MM5 train or semi-VOST (volatile organic sampling train),
is conceptually very similar to the SASS but operates at a lower
flow rate, usually 14 to 28 L/min (O.S to 1 ftVmin). The MM5,
shown in Figure 8.7, does not include particle-sizing cyclones and
is usually constructed of glass rather than stainless steel. The
MMS results from a very simple modification of any of the commer-
cial sampling trains available that conform to the requirements of
EPA Method 5. The sorbent module with cooling capability is
simply inserted between the filter and the first impinger. The
soibent module must be positioned vertically so the gas and any
condensed liquids flow downward through it.
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The sorbent of choice for most sampling jobs for both the
SASS and MM5 is XAD-2. Johnson (14) presents a discussion of the
reasons behind this choice, as well as of sorbent module placement
in the train.
Because of its more convenient size, glass construction, and
ready availability, the MM5 is usually chosen over the SASS for
incinerator sampling unless larger samples are needed for lower
detection limits or extensive analysis requirements.
Either the SASS or MM5 provides collection ability for par-
ticulate material, acid gases snch as HC1, gaseous metal compounds
(if appropriate collection liquids are chosen), medium-boiling
organic compounds (b.p. greater than 100 to 300*C), and high-
boiling organic compounds (b.p. greater than 300*C). Organic
compounds with boiling points between 100 and 120*C require
individual attention during the sampling planning stage and may
require decreased sampling times to prevent volumetric break-
through. Volumetric breakthrough is Delated to the migration
rate of sorbed material through unsaturated sorbent beds This
important concept has been discussed further (14).
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Considerable field experience has been gained with the SASS
and MN5 trains. In recent years, much of the confidence in these
trains' ability to collect organic substances rested on knowledge
of the behavior of sorbents with respect to collection and
recovery. Schlickenrieder et al. (15), discuss this point in more
detail. Recent validation studies for selected compounds show
excellent collection and recovery and reinforce the general
conclusion that the trains are effective (16-18). The MM5 and
SASS are not generally quantitative collection trains for organic
compounds with boiling points lower than 100*C. For these low-
boiling compounds, the recommended methods are plastic sampling
bags, glass sampling bulbs, or the newly developed VOST. Because
the ambient air at incinerator sites may exhibit relatively high
levels of volatile organic compounds, the difficulty is greatly
increased in obtaining an uncontaminated sample of low-
concentration volatile compounds from the stack. All sampling
methods for low levels of volatile compounds are subject to poten-
tial contamination and require application with a great deal of
care, as well as adequate blanks. All of the above methods have
shortcomings, but they are much less severr. than the shortcomings
and limitations of alternate approaches (12).
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The VOST is shown in Figure 8.8. This train and the analysis
approach applied to the samples resulting from its use were devel-
oped to address stack concentrations as low as 0.1 ng/L. A
sorbent tube containing 1.6 g of Tenax is positioned early in the
train to remove organic compounds from the gas and liquid stream
as soon as possible. A second sorbent tube containing 1 g of
Tenax and 1 g of charcoal follows the condensate collector as a
backup in case of breakthrough. The charcoal provides added
stopping power for compounds with very low boiling points such as
vinyl chloride. The train was designed to use five pairs of
sorbent tubes sequentially (plus one pair for range finding), each
operating for 20 min at 1 L/min. The ability to concentrate the
organics from all five sets of tubes onto one analytical tube and
subsequently heat-desorh into a GC or GC/HS makes is possible to
detect very low levels of compounds relative to their stack gas
concentration. For higher stack gas concentrations, the VOST can
and sometimes must be operated at lower flow rates and longer
sampling times (limits 0.251 pra for 8 min). This piece of equip-
ment should be useful in a number of operation modes, as long as
excessive volumes of gas are not pulled through a single tube,
because compounds with low boiling points break through the
sorbent after relatively low volumes.
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The development and use of the VOST has been discussed in
several publications (7_, 14, 19-21). References 7 and 20 are
particularly helpful to users of this train. Preliminary evidence
that the train is effective is given in these references, and an
EPA validation project further supports that position (22, 23).
Various types of plastic sampling bags have been used with
mixed results. This approach can yield good results, but the
sampling and storage characteristics of the specific compound,
relative to the specific types of bags to be used, must be well
known. For examp'e, organic compounds such as alcohols usually
exhibit poor storage characteristics in bags (24). Also, field
blanks must be included in the sampling strategy, because all
known methods for storing and shipping volatile organic compounds
collected from incinerators could allow potentially severe
contamination of samples in the field and during transit.
When relatively high concentrations of volatile compounds are
sampled, glass sampling bulbs with secure seals may be the best
sampling method. Although somewhat inconvenient and lacking in
sample-concentrating ability, the glass bulbs do show better
sample storage characteristics than plastic bags (24). Because
samples cannot be integrated easily with glass bulks, they may not
be appropriate for regulatory purposes unless samples are taken
in great numbers.
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In addition to the methods discussed, special procedures may
be necessary for certain pollutants. Formaldehyde is an example
of a compound that requires special handling (25). Harris
et al. (10) give guidance for such cases. A number of other
general sampling approaches exist (13), but are less satisfactory
and have not been recommended.
Sampling methods have been discussed that are generally
applicable to incineration and to processes closely related to
incineration, such as cofiring of waste in industrial boilers
and burning of contaminated heating oil. Although some of the
methods are relatively new and all require a great deal of care
and attention, excellent results can be produced through their
application.
Obtaining a representative sample from the stack, partic-
ularly in the case of organic emissions, is a complicated and
technically difficult process. The most consistent and well-
defined result will be obtained by following detailed, written,
validated procedures (e.g., 7). The tendency to modify such
procedures or replace then with new ones should generally be
resisted.
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8.2.3 Sampling Solid and Liquid Effluents from
Combustors and Control Devices
The methods and equipment previously discussed for use with
waste combustion products will often be applicable (_7, 10) to
sampling solid and liquid effluents. In addition, liquid
samples mvet sometimes by taken from taps. In certain instances,
sampling dit'Iculties may require special operation of the equip-
ment. Bottom ash from combustors is often difficult to collect
and particularly difficult to relate to a given charge of waste.
Sometimes bottom ash can be obtained from pilot units by shutting
down operation and collecting the ash from an entire run.
Si '.iar operations have been carried out to obtain boiler tube
soot for an entire batch of cofired waste.
8.2.4 Sample Containers, Shipping and Storage
Every step in the sampling and analysis chain of events is
critical and cannot be carried out carelessly without detriment
to the final result. Container selection guidance given in the
references (7_, 10) usually recommends glass containers protected
against light and excessive heat. Glass is usually recommended
because it is relatively inert and easy to clean thoroughly. In
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certain circumstances, plastic containers may be preferable and
are recommended. The containers must also have secure seals to
prevent both sample loss and contamination.
Sample preservation techniques discussed in the literature
(7_, 26, 2H) are specific to the various methods to be used for
analysis. Organic pollutants are generally not treated by addi-
tives for preservation purposes but are cooled and protected
from light.
Shipping must always be done in compliance with Department of
Transportation regulations. In addition, thought must be given
to acceptable delays before analysis and potential for degradation
of the samples. For example, it is not acceptable to transport
samples from a VOST in the same truck compartment with organic
solvent cans used for spiking waste or cleanup field operations.
Storage conditions after receipt of the samples from the
field are just as important as those during shipping, and they
follow many of the same guidelines. Organic compounds are often
refrigerated and are always protected from light. Other samples
should also be treated with care and not exposed to extreme
conditions or high levels of chemical contamination.
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8. Sampling and Analysis of Hazardous Wastes
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8.2.S Quality Control and Quality Assurance
Although QA/QC procedures and planning are more often associ-
ated with analysis, they should also be used during the planning
and implementation of the sampling operation. The use of field
blanks field spiking procedures, and other aspects of QC have a
great deal of influence on field sampling operations. The
references (7_, 10) have detailed discussions of this important
subject. Audit procedures and samples have been developed for
some of the sampling methods (28, 29), and their use is highly
recommended even when not actually required.
8.2.6 Safety
Safety of the personnel involved is the most important con-
sideration in any sampling activity. The hazardous waste involved
may require special clothing or equipment such as respirators.
Several of the references have more detailed discussions of this
subject (7^, 2» 10)» Efforts should also be made to ensure that
safety procedures are not violated during field sampling, regard-
less of the delay that might ensue. Perhaps the most essential
part of the safety program dealing with hazardous-waste-related
sampling is a thorough and effective personnel training program.
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This should include general training in procedures, as well as an
introduction to possible risks to be encountered. In addition, a
specific safety-oriented discussion should be carried out with the
field crev before each sampling trip, which should deal with
specific wastes and hazards that are likely to be encountered at a
particular site.
8.3 ANALYSIS OF HAZARDOUS WASTE AMD RELATED PRODUCTS
8.3.1 Background
Before any generalizations are made about the analysis of
hazardous waste, some explanation as to the magnitude and com-
plexity of the overall problem seems warranted. We must
consider such diverse factors as the number of wastes generated,
the physical states of the wastes, handling and treatment of the
wastes, number of potential compounds, toxic or otherwise, and the
routes of entry into the environment. According to EPA estimates,
more than 200,000 generators produce over 264 million metric tons
of hazardous toxic waste annually in the United States. This
waste, if improperly managed, poses a serious threat to human
health and the environment. More than 60,000 chemicals are now
in use, and untold others are being registered each day (30).
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8. Sampling and Analysis of Hazardous Wastes
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Furthermore, literally thousands of unregistered trace chemicals
are associated with tha registered chemicals in use. Fortunately,
most of these chemicals are not considered harmful and many
enhance the quality of life. Of those that are considered hazard-
ous substances, many are considered essential in the manufacturing
processes leading to useful products, and others are simply the
by-products of a specific process. On the other hand, a signif-
icant number of registered hazardous substances are no longer in
commercial use.
A wide range of technologies exists that can concentrate,
destroy, or immobilize industrially generated hazardous wastes.
The commercially available treatment technologies can be catego-
rized into five major types of treatment; physical, chemical,
biological, thermal, and fixation/encapsulation. Treatment
processes for hazardous wastes perform the following functions:
volume reduction, component separation, detoxification, destruc-
tion, storage, and material recovery. Because no single process
can perform all these functions, several different processes must
usually be linked in series for adequate treatment. Additionally,
selection of appropriate treatment methods depends on the nature
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of the waste, form or physical state of the waste, the volume of
the waste, relative economics of the treatment methods, and
government regulations.
Incineration has long been recognized as one of the best
demonstrated and commercially available technologies for waste
destruction. Industrial, high-temperature processes can also
destroy certain hazardous waste. A gradual shift to incineration
as a preferred method of hazardous waste treatment has resulted
from Federal and State legislation regulating the disposal of
hazardous waste. It is estimated that about 740 incineration
facilities are currently operational, 40 of which are commercial
facilities. Industrial, high-temperature processes can also
destroy certain hazardous wastes. Thermal destruction is cur-
rently used to dispose of about 2 to 4 percent of the hazardous
waste generated each year (31, 32).
Methods of measuring and defining toxic and hazardous emis-
sions in the environment have been developed as a result of the
T.. xic Substances Control Act (TSCA), the Resource Conservation and
Recovery Act (RCRA), and the efforts of EPA and industry. The
term "hazardous substance" has a very specific meaning according
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to the Comprehensive Environmental Response, Compensation and
Liability Act (CERCLA). Section 101 (_14) of CERCLA defines a
hazardous substance as follows:
1. Any substance designated pursuant to Section 311(b) of
the Clean Water Act (CWA)
2. Any hazardous vaste having characteristics identified
under or listed pursuant to Section 3001 of the Solid
Waste Disposal Act, otherwise known as the Resource
Conservation and Recovery Act (RCRA)
3. Any toxic pollutant listed under Section 307(a) of the
CWA
4. Any hazardous air pollutant listed under Section 112 of
the Clean Air .Vet (CAA)
5. Any imminently hazardous chemical substance or mixture
with respect c^ which the Administrator of EPA has taken
action pursuant to Section 7 of the Toxic Substances
Control Act (TSCA)
6. Any element, compound, mixture, solution or substance
the Administrator determines to be hazardous pursuant to
Section 102 of CERCLA
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There are currently 717 hazardous substances (HSs) composed
of 611 unique chemical compounds and 106 waste streams (33). This
total does not include chemicals or mixtures that exhibit charac-
teristics of ignitability, corrosivity, reactivity, or toxicity
according to 40 CFR 261.20. The toxic and hazardous category
contains many different substances; however, organic compounds are
the most complex and difficult to measure. The selection of
appropriate analytical methods depends on a number of important
considerations. These include the compounds of interest, the type
of waste, the source type, instrument selectivity/sensitivity, and
the desired level of detection. Consideration of cost, though
secondary, as well as the intended use of the data, can be equally
important in the selection process. The complex nature of organic
compounds dictates the complexity of the analytical methods.
Also, organic substances can enter the environment via gaseous,
liquid, or solid media. Although each medium may require differ-
ent sampling techniques (Section 8.2) and sample preparation
techniques, the analytical methods for most samples contain many
steps that are essentially the same.
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This section addresses the considerations that are most
important in selecting analytical methods for the analysis and
management of hazardous waste. Each step of the various pro-
cesses, from the testing of a waste to the disposal of the waste,
must be monitored to ensure that each process is environmentally
sound and protects the environment. The analytical methods
applicable to the analysis of different types of hazardous waste
are described or summarized in the following sections and tables.
A brief description of the tcchology, a summary of each method,
and pertinent references are included.
8.2.3 Analytical Methods
Because organic hazardous waste is complex, no single analyt-
ical technique is applicable to all wastes. For most samples,
the analyst should employ proven analytical techniques that are
selective and sensitive. The most universal methods for trace
analysis are gas chromatography (GC). liquid chromatography (LC),
mass spectrometry (MS), and a combination of the methods. More
specifically, these combinations include gas chromatography/maas
spectrometry (GC/MS) and liquid chiomatography/mass spectrometry
(LC/MS).
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The minimum detectable quantity (MDQ) for GC depends on the
detector used and ranges from 10~9 to 10—13 g per injection
(34). Samples must be volatile (at least 20 torr at 300*0) but
can be gases, liquids, or solids. High-molecular-weight
compounds, some ionic compounds or highly polar compounds, and
thermally unstable compounds cannot be analyzed directly by GC.
In some cases, derivatization or pyrolysis techniques can extend
the useful range of the GC. Gas chromatographs are widely used,
because they (1) are not expensive, (2) are easy to operate, and
(3) give excellent quantitative results; however, GC can only
confirm the identity of a substance by retention time alone. This
is a major concern when complex waste samples are analyzed and
several components could have the same retention time. The MS in
a total ion current (TIC) scanning mode may be used to identify a
compound. If the identity of a compound is known, selected-ion
monitoring (SIM) can be used for quantitation to extend the MDQ
and for confirmation and quantitation. The sensitivity of the MS
ranges from 10"9 to 10"12 g. Samples that can be analyzed by
GC can be analyzed by MS. The GC/MS is a universal technique,
handling all sample types, and it is specific in that it will
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usually confirm the structure (identity) of a compound. GC/MS is
preferred for trace organic analysis, and the instrumentation is
readily available, but it is moderately expensive and requires an
experienced operator. It has been estimated that approximately 20
percent of all organic compounds can be determined by GC/MS (35).
Fortunately, of those compounds currently of environmental con-
cern, approximately 80 percent are amenable to GC/MS analytics.
Liquid chromatography is recommended for compounds not amena-
ble to gas chromatography. the application of high-performance
liquid chromatography (HPLC) to the analysis of waste samples has
increased significantly. HPLC can be used for identifying a vide
range of less volatile compounds not amenable to GC. Chemically
bonded stationary phases for HPLC have greatly improved the sepa-
ration of a vide variety of compounds. Samples can be liquid or
solid, organic or inorganic, and range in molecular weight from 18
to 6 million (34). Selectivity is dependent upon sample type and
the detect*.r used. The 0V detector is considered the most uni-
versal and can measure 10~* g of most species. Aliphatic hydro-
carbons are a notable exception because the UV detector is less
sensitive to this class of compounds. This lack of sensitivity for
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hydrocarbons can frequently be used to advantage, because most
environmental samples contain a higher percentage of such coo-
pounds than of the analyte of interest. Other LC detectors are
more selective and sensitive. For example, for selected com-
pounds, the fluorescence detector can measure 10~12 g, and the
electrochemical detector can measure 10 lo g. Although not yet
widely used in waste analyses, the LC/MS combination separates
complex mixtures and extends the selectivity of the MS to a large
class of organic compounds not amenable to GC/MS analysis.
Table 8.2 summarizes the instrumental techniques and detectors
widely used for trace analysis.
Reliable analytical measurements of environmental samples
are an essential ingredient for making sound decisions involving
many facets of society, which include advancing technology,
safeguarding the public health, and improving the quality of the
environment. The American Chemical Society's Committee of
Environmental Improvement (CEI) charged its subcommittee on
Environmental Monitoring and Analysis with the task of developing
a set of guidelines to improve the quality of environmental
analytical measurements (36). The guidelines aid in the evalua-
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8. Sampling and Analysis of Hazardous Wastes
8-35
tion of analytical measurements and in the intelligent choice of
methods that meet the requirements of a specific measurement.
Analytical objectives often require the measurement of parts-per-
mit I ion levels in hazardous waste samples and parts- per-biliion
and even parts-per-trillion levels in hazardous waste combustion
effluent samples. Advances in analytical methodology continue to
lower the levels of detection to meet these needs. Many factors
are of critical importance at these levels and influence the
outcome and reliability of environmental measurements. Good
planning is essential to ensure that the results are valid and
provide a basis on which a process or regulatory decision can be
made. The analyst cannot assume that the person requesting an
analysis will also be able to define the objectives of the analy-
sis properly.
A protocol that describes the analytical process in detail
should include a description of the quality assurance and quality
control requirements, the sampling plan, the analytical methods,
calculations, and documentation and report requirements. If
analytical data are to be used for a screening program or to
adjust an operating parameter, an unvalidated method may be
adequate. If on the other hand, a regulatory compliance is
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involved, a validated analytical method is usually required. To
validate a method, the CEI committee recommended that a minimum of
three different concentrations of calibration standards be
measured in triplicate. The concentrations of the calibration
standards must bracket the concentration of the analyte in the
sample. No quantitative data should be reported beyond the range
of the calibration of the methodology. Internal standards (refer-
ence materials) are frequently used for quantitation. Surrogates
are frequently used for spiking to determine recovery efficiency
during sample preparation. Internal standards are added prior
to analyses. Both types of reference materials are chosen to
simulate the analyte of interest.
Selection of a proper analytical method is one of the most
important factors influencing the reliability of the resulting
data. Measurements should be made with tested and documented
procedures. Furthermore, each laboratory and analyst must evalu-
ate the methodology by using typical samples to demonstrate
competence in the use of the measurement procedure.
To address the analyses of both hazardous wastr and products
from the combustion of hazardous waste, some assumptions are
necessary. Namely, the methods cf collection and sample prepara-
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standards, or other materials. These physical and chemical treat-
ments not only add complexity to the analytical process but are
potential sources of contamination, mechanical loss, bias, and
variance. Therefore, sample preparation should be planned care-
fully and documented in sufficient detail to provide a complete
record of the sample history. Further, samples taken specifically
to test the quality assurance system (i.e., quality assurance
samples) should be subjected to these same preparation steps.
The analyst must recognize and be aware of the risks that are
associated with each form of pretreatment and rake appropriate
preventative action for each. This may include reportin* : cor-
recting for, or possibly removing interferences from the analytes
of interest by modifying the protocol. Mi changes in the proto-
col must be documented. In most cases, sample stabilization
(either by pH adjustment or by quenching of dissolved chlorine),
depending on the compounds present, is not necessary if the sam-
ples are :o be extracted within 48 h of sampling. However, sam-
ples containing phenols and benzidine derivatives require immedi-
ate stabilization, and samples containing metals and cyanides
must be stabilized upon arrival at the laboratory. Both can be
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8-39
stabilized by pH adjustment. Samples are generally stored at
4 *C. Purgeable samples should be analyzed within 7 days of
collection or as requested in the protocol (7 to 14 days).
Extractable organic compounds must be extracted within 7 days
and analyzed within 30 days of collection. Metals and cyanides
should be analyzed within 30 days.
Ideally, samples of source combustion emissions should be
Kept at low temperatures and analyzed very rapidly after collec-
tion to minimize losses of compounds by vaporization and reaction.
Samples should be protected from direct light during and after
collection. Most of the literature on source sampling has not
provided information on sample preservation. Holding time and
preservatives for water pollutants and other analytes have been
published in the Federal Register. Details of sample handling
containers, preservation, and holding times for hazardous wastes
are documented in Chapter IV of the SW 846 document (7)*
Many organic samples continue to be reactive after sampling.
Therefore, a sample, when fresh, may yield different values for
the analyte than the same sample after it has been stored.
Because of the complexity of hazardous waste samples and the
limited selectivity of many analytical methodologies, inter-
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ferences are frequently encountered during analysis. Controls to
verify that interferents are not present must be used, atjd
appropriate cleanup procedures should be included to eliminate the
interferent.
In the analytical process, the recovery of analytes is
influenced by factors such as concentration of the analyte,
sample matrix, preservation, and time and temperature of storage.
In certain cases, compounds can be lost during extraction. Hexa-
chlorocyclopentadiene has a strong tendency to be absorbed on
glass and can be lost during liquid-liquid extraction. The sam-
pling medium can also affect the composition of organic emissions.
Artifacts have also been reported when Tenax GC is used as the
sorbent in source sampling (37). There is also evidence for the
decomposition of polynuclear aromatic hydrocarbons (PAHs) col-
lected on fiberglass filters commonly used in source sampling
systems. Teflon or Teflon-coated filters, however, appear to be
relatively inert (38). Other problems are often encountered in
sample preparation. Sample contamination can occur from improp-
erly cleaned glassware, improper storage and sampling handling,
impurities in solvents, and carrier gas contamination; and cross-
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contamination can occur from analyzing high- and low-level samples
in succession. If a high-level sample is run, a blank should be
run to check for carryover. Cross-contamination can also occur
when volatile samples are prepared and analyzed in a laboratory or
eve . in the same building where liquid-liquid extractions are
performed (9_, 39). Any volatile solvent in use in the laboratory
is a potential candidate to contaminate volatile samples. Blank
samples do not eliminate the problem but do help to identify the
problem. Corrective action is frequently required before sample
analysis can continue.
Emulsions and foaming may occur during sample preparation and
analysis. Emulsions can be broken by stirring, filtration,
centrifugation, cooling, or simply allowing them to stand for
longer periods of time. Foaming can be reduced by antifoam agents
or by specially designed purge vessels or in some instances by
adding cleaned, glass-melting-point capillary tubes to the purge
vessel. Matrix effects can cause a wide variability in recoveries
with organic compounds. Therefore, to be valid, recoveries of a
spike standard must be determined in the same matrix as the
sample (39).
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8.3.4 Analysis of Hazardous Waste
The overall strategy for analyzing hazardous waste includes
procedures to determine characteristics of the waste and proce-
dures to determine the composition of the waste. Test procedures,
or supporting documentation, is required in each of four major
areas.
• waste characteristics
• proximate analyses
• survey analyses
• directed analysis
Details of the procedures and recommendations for conducting
these tests are given in the literature (J^. 10). An overview of
the analytical approach for waste characterization is given in
Figure 8.9.
8.3.4.1 Characteristics
Wastes are classified as hazardous if they exhibit any of the
following characteristics:
• Toxicity
• Corrosivity
• Reactivity
• Ignitability
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The Extraction Procedure (EP) Toxicity Test is currently used
to determine if the waste exhibits the characteristic of toxicity.
The test involves a leaching procedure used to simulate the
aqueous leaching of a toxic chemical when t.»e waste is land
disposed. The EP toxicity characteristic sets regulatory levels
for eight metals, four pesticides, and two herbicides (National
Interim Primary Drinking Water Standards have been established).
Any waste that exceeds the EP toxicity thresholds (Table 8.5) is
considered hazardous. Details of the EP toxicity procedure are
given in Method 1310 in the SW 846 document (.7)• A proposed new
rule would revise the EP toxicity test to include regulatory
levels of 38 additional compounds. The new Toxicity Character-
istic Leaching Procedure (TCLP) expands the leaching to model the
behavior of volatile and aemivolatile organics. The complete
waste evaluation for TCLP will require two extractions, one for
volatile and semivolatile compounds and one for metals. Volatile
compounds must be extracted in a zero headspace extractor.
Contaminants regulated under the proposed TCLP and regulatory
levels are given in Table 8.6.
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EPA has proposed using the TCLP for the Land Disposal
Restrictions Program under RCRA Subtitle C. The list of Land
Disposal Hazardous Constituents is given in Table 8.7. Procedures
for the analysis of leachates are described under directed analy-
sis and are based on standard methods established for priority
pollutants. Methods for determining ignitability (Methods 1010
and 1020), corrosivity (Method 1110), and reactivity are given in
the SW 846 document (7).
8.3.4.2 Directed Analyses
Directed analyses allow quantitative measurement of desig-
nated principal organic hazardous constituents (POHCs) in a vari-
ety of samples. The POHCs listed in 40 CFR Part 261, Appendix
VIII, possess a broad spectrum of physical and chemical proper-
ties. Because of the high degree of complexity in the field of
organic analysis and the parallel complexity of hazardous waste,
the only suitable approach to quantitation and confident identifi-
cation of specific compounds is by either gas or liquid chromatog-
raphy. Each OC and LC detection method is based on a different
operating principle and responds to different compound classes.
When the MS, a highly sophisticated detector, is coupled with the
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GC, it identifies and quantifies individual compounds by their
mass spectra and retention time. The GC/HS analysis procedure is
the method of choice for organic analysis and has been designated
for the determination of many of the constituents from the
Appendix VIII list. This technique, is selective and sensitive,
and the use of high-resolution capillary columns improves the
separation of complex mixtures. Most Appendix VIII compounds are
amenable to GC/MS analysis. Other compounds may require analysis
by HPLC, and a few other eoapounds may require compound-specific
or compound-class-specific procedures. The GC/HS and LC analysis
of organic constituents is briefly summarized below and discussed
in Section 8.3.6. Other compound-specific analytical procedures
are not discussed in this chapter, but all compounds in Appendix
VIII must be considered in the listing of hazardous waste.
Analytical methods using these techniques for hazardous waste
have evolved from the experience profile of priority pollutant
analysis.
By minimizing the number of analytical procedures and
enlisting previous experience with priority pollutant analyses,
the number of compounds that can be analyzed by a single method
ysr
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is maximized. Some of the SPA "600" methods shown in Table 8.8
have been adapted to hazardous waste analysis. Methods 624 and
625 have been extended to the determination of many Appendix VIII
compounds (5-7, 40). For example, the recommended method for
volatile organic compounds is similar to EPA Method 624, and the
method for extractable (semivolatile) organic compounds is similar
to EPA Method 625. Table 8.9 lists toxic organic compounds that
are designated as priority pollutants, Superfund compounds
(CERCLA), and selected Appendix IX compounds. This table
illustrates that 115 compounds are common to all lists.
The analysis method for volatile POHCs is identical to the
method specified in EPA Method 624 and SW 846 Methods 5030 and
8240. Volatile organic compounds can be determined by these
methods after appropriate sample-matrix-dependent pretreatment, in
a wide variety of samples including water, leachates, wastewater,
hazardous waste, and soils. This method uses a purge and trap
(PAT) system with an inert purge gas to remove the volatile
substances from the waste and collect them on a sorbent trap. The
collected volatile compounds are then thermally desorbed from the
sorbent cartridge to the GC column (SP-1000 on Carbopak B) and
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analyzed by OC/MS. As with all analytical procedures employing
conplex matrices, the purge efficiency for each volatile compound
of interest must be determined.
The method for analyzing semivolatile extractable compounds
is equivalent to EPA Method 625 and SW 846 Methods 8250 and 8270,
and its resolution and sensitivity are increased by using an SE-54
bonded, fused-silica capillary column, recommended in Method 8270.
These methods are based on the acid/base extraction of the waste
with aliquots of a suitable organic solvent, SW 846 Methods 3500
and 3550, and subsequent concentration of the extracts to a suita-
ble volume. The acid and base extracts are usually combined for
analysis. Some organic liquid wastes may be prepared for screen-
ing analysis by dilution with solvent and direct injection
(Method 3580). Microliter volumes of sample extracts are injected
onto the fused-silica capillary column by using splitless (or
split) injection techniques or on-column injection. The mass
spectrometer is usually operated in the electron-impact (El) mode
and the full-scan mode to produce mass spectra for identification.
Selected surrogates and internal standards must be added to each
sample at the appropriate time as detailed in each procedure.
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A generalized HPLC/UV method can be used for some other com-
pounds not amenable to GC/MS analysis and for some compounds such
as PAHs aaenable to analysis by both procedures. The generalized
HPLC methods are based on the use of reversed-phase C^, columns.
Some compounds are not amenable to the generalized HPLC procedures
and require specific HPLC procedures (]_, 10). A UV detictor is
recommended for use with screening methods because the detector
can measure a wide range of wavelengths from 190 to 600 nm. For
screening a sample, most procedures recommend that the initial
wavelengths be set at 254 nm. For specific compounds, other wave-
lengths offer both increased sensitivity and selectivity. Various
procedural options for the HPLC method have been described
<£. JO).
8.3.5 Analysis of Hazardous Waste Combustion Products
Effluents from hazardous waste combustion must be analyzed to
determine if POHCs selected for a trial burn are destroyed in
the incineration process and meet the required destruction and
removal efficiency (ORE) of >99.99Z established for most com-
pounds. Methods for sampling stack effluents were discussed in
Section 8.2.3. Other associated streams such as process scrubber
water and solid residues (ash) must be analyzed either to deter-
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mine the presence of POHCs or to determine other residual
contaminants relating to safe and regulated disposal of the
products. The analysis of incinerator effluents involves the same
considerations as the analysis of noncombusted hazardous waste.
As detailed in Section 8.2.3 the method of sample collection is
different; therefore, instead of one composite sample, as is the
norm for hazardous waste, there may be several different samples
from the effluent of a combustion source and other process and
residue samples.
Before combustion effluents are analyzed, the wast* feed must
be analyzed. Samples of waste must be taken in appropriate zero-
headspace bottles (40-mL VOA vials) for volatile analysis. A
second composite sample is required for analysis of semivolatile
compounds. The VOA samples are analyzed by the purge and trap-
GC/MS procedure, and the semivolatiles are extracted and analyzed
by GC/MS as described earlier.
The waste feed, particulate matter, probe wash, and ash
residues from combustion may be analyzed for metals (Table 8.10),
if metals are present in the hazardous wste. Digestion and
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analysis procedures are given in SW 846 methods. SW 846 Method
3010 is recommended for acid digestion for flame atomic absorption
spectrometry (AAS) or Method 3020 for acid digestion for furnace
AAS. The metal-containing constituents and the metals on the
Appendix VIII list are analyzed either by AAS or inductively
coupled argon plasma (ICAP) emission spectroscopy techniques (_7) -
Table 8.11 summarizes recommended SW 846 methods of AAS. The
recommended method for ICAP analysis of multielements is SW 846
Method 6010. The sample digestion techniques depend on the
instrumentation employed for the analysis. Mercury is analyzed by
a cold vapor technique. The ash may also be analyzed for selected
organic compounds, normally for those POHCs that are designated
for analysis in the stack effluent.
The ash is prepared for organic analysis by Soxhiet extrac-
tion with methylene chloride and concentrated in a Ruderna-Danish
apparatus and then analyzed by GC/MS or HPLC methods. The ash
extract may also be analyzed or screened for other organic com-
pounds by the same general procedures.
Scrubber water and other process waters are analyzed for the
same organic compounds designated in the trial burn. These may
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include both volatile compounds and semivolati'e organic
compounds.
The volatile compounds from stack effluents are collected
with a VOST system (8.2.2). The volatile POHCs in the stack gas
effluent are collected on several pairs of sorbent tubes. The
sorbent tubes are thermally desorbed into the purge vessel of a
purge and trap instrument and analyzed as described for hazardous
waste by EPA Method 624 (SW 846 Method 8240). The purge vessel is
necessary to prevent excess water from the sorbent tubes from
entering the GC/MS system. The VOST analytical method is directly
applicable to compounds with boiling points from 30 to 100*C but
with minor modifications can be extended to some compounds with
boiling points above and below this range. Water-soluble com-
pounds may give poor recovery with this method, and extra care
should be taken to determine if the data are acceptable for these
compounds or, alternately, select a new or modified procedure
(4^7, ^0, 38).
The semivolatile compounds are collected with a comprehensive
sampling train as described in Section 8.2.2. The samples for
analysis consist of probe wash, particulate matter, scrbent
-------
Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-52
trap, and condensate. Each sample must undergo sample preparation
including extraction and concentration (SW 846 Methods 3500 and
3550) before analysis. The extracts from the component parts of
the sampling system may be combined for analysis by GC/MS by EPA
Method 625 (SW 846 Method 8270) or for specific compounds by HPLC.
Individual extracts may be analyzed if the collection efficiency
of a particular part of the sampling system is being evaluated.
Figure 8.10 is an overview of the analysis scheme for stack gas
samples from the VOST and the MM5 sampling trains (10).
EPA does not currently regulate the emissions of most toxic
thermal reaction products commonly called products of incomplete
combustion (PICs). For the EPA program, compounds *re considered
PICs if they are regulated compounds (Appendix VIII) that are
detected in the stack emissions but not present in the waste feed
at concentrations >100 ppm. In many cases, a PIC may also be
designated as a POHC. The formation of PICs that are monitored as
POHC emissions results in anomalously low DRSs. Field studies by
Trenholm et al. (3) and Castaidine et al. (41) have shown that
PICs are emitted from hazardous waste thermal destruction systems.
Some experimentally observed PICs are shown in Table 8.12.
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-53
Current data suggest that for thermal destruction facilities where
high degrees of ORE have been achieved for POHCs, PIC emissions
are also low (32). Thus, when a POHC is selected, consideration
must be given to the potential for the POHC to also be a PIC. For
most PICs, the analytical methodology is similar to that described
for POHC analysis. Dioxins and furans are notable exceptions
and require specific analytical procedures (10, 42-44).
8.3.6 Use of Surrogates
To simplify the overall analytical approach, it ha.- been
suggested that surrogates be used to evaluate the performance of
an incinerator. A compound may act as a surrogate for a specific
waste feed, or for any waste feed and any incinerator. An ideal
surrciflte would be nontoxic and easily monitored and more stable
than any other compounds in the waste. Proposed surrogates
include total unburned hydrocarbons (TUHCs) and carbon monoxide
(CC), but these may not correlate with ORE. A listed compound in
the waste or a thermally stable compound added to the waste feed
may serve as a surrogate. Selection of a single organic compound
(or several specific compounds) as a surrogate for evaluation of
DRE would greatly simplify monitoring requirements. Gas-phase
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-54
thermal stability has been proposed as an alternate to heat of
combustion as a ranking scheme for selecting a surrogate compound
slightly acre stable than any listed compound intended for
incineration. Some samples of thermally stable compounds are
acetonitrile, hexachlorobenzene, monochlorobenzene, tetrachloro-
ethylene, and trichloroethylene. Halogenated compounds such as
CF^, C2F6, C3F8, CF3Cl, C2F3C13, and SFg, have also been suggested
as possible additive candidates (11, 45, 46).
Emissions of CO and TUHCs may not correlate with ORE but do
tend to act es indicators for upset conditions. Selecting a
thermally stable component of waste feed, or a thermally stable
additive, appears to be scientifically defensible and technically
feasible. Protocols for the analysis of a few approved surrogates
would be more specific and greatly simplify the assessment of
incinerator performance.
8.3.7 Documentation
Analytical measurements should be documented to provide easy
access to information to support all claims for the results.
Laboratory records should be retained in a permanent file for a
-------
Larry D. Johnson
Std HB Cor Hazardous Haste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
length of time set by the government or other legal requirements.
All d«r« must bs recorded in laboratory notebooks (bound notebooks
preferred) and cross-referenced to raw data such as chromatograms
and mass spectra stored in the raw data file.
Environmental management has a strong, documented technical
data component. A major problem is the conversion of rav data
into information needed for decision making in hazardous waste
management. At present the reporting of results remains a paper-
intensive, manual system. For example, in 1985 the EPA Contract
Laboratory Program consisted of approximately 50 laboratories
analyzing samples at a rate of 40,000 per year. Current
requirements for the delivery of data on a single sample requires
a 2 1/4-in.-thick stack of paper. At this rate, EPA will have a
stack of paper containing highly technical data 1 1/2 miles high
to examine this year. These data must be converted into useful
information to support environmental management. In 1983, the
idea for an improved system for handling and processing data was
suggested. Data would be transmitted by electronic or magnetic
means and machine-read into appropriate integrated computer data
bases (47). A good start has been made by EPA in evaluating the
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-56
feasibility of electronic data transfer, thus substantially
improving the efficiency with which EPA handles data. Data
assessment for evaluating hazardous waste cleanup will be faster
and more accurate in the near future. This approach may be
necessary for day-to-day management of data records from waste
management facilities.
8.3.8 Quality Assurance/Quality Control
The quality assurance (QA) component of the analysis of
environmental samples is of the highest priority. Data from the
analysis of soil, air, drinking water, wastewater, sludge, and
hazardous waste must be scientifically valid, defensible, and of
known and acceptable accuracy and precision. Thus, the QA program
must contain procedures for program management and personnel
responsibilities, facilities and equipment, data generation and
processing, data quality assessment, and corrective actions.
Individual QA programs may vary depending upon the nature of the
material to be analyzed and the intended use of the final data.
However, certain aspects are common to all situations.
Guidance for developing adequate QA program plans is availa-
ble (48). The QA program plan stipulates the QA policies, objec
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disoosal
6. Sampling and Analysis of Hazardous Wastes
8-57
tives, management structure, responsibilities, and procedures for
a total QA prograa for the organization performing analytical
services. Included in the program plan is information concerning
procedures to ensure the generation of reliable data; processes
for collecting, reducing, validating, and storing data; procedures
for assessing data quality (accuracy and precision); procedures
for performing corrective actions; and the schedule for implemen-
tation of the requirements.
The scope of a program plan is usually general. However, a
QA project plan gives a more detailed description of how the
analytical organization will produce quality data for a specific
analysis. Every project that involves environmentally related
measurements should have a written and approved QA project plan.
Guidance for preparing QA project plans is available (49).
A QA project plan may contain one or more of the following
items, if they are appropriate for the specific contract.
• Title page with provision for approval signature
• Table of contents
• Project description
• Project organization and responsibility
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Larry D. Johnson
Std HE for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-58
• QA objectives for measuring data in terms of precision,
accuracy, completeness, representativeness, and
comparability
• Sample procedures
• Calibration procedure and frequency
• Analytical procedures
• Data reduction, validation, and reporting
• Internal quality-control checks and frequency
• Performance and system audits and frequency
• Preventive-maintenance procedures and schedules
• Routine procedures for assessing data precision,
accuracy, and completeness for specific measurement
parameters involved
• Corrective action
• G:ality-assurance reports to management
QA project plans are usually prepared in a document-control
format consisting of information (i.e., section number, revision
number, date of revision, and page number) in the upper right-hand
corner of each page of the project plan. All 16 items described
previously may be considered and addressed. The level of QA
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Larry D. Johnson
Std KB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Hastes
8-59
depends on the project and the end-use of the data that are
produced. Specific procedures to assess precision and accuracy
on a routine basis during the project are described in each QA
project plan (^t 10).
8.3.9 Conclusion
The disposal of wastes will remain regulated with greater
emphasis on problem wastes an«. extremely hazardous wastes as they
are identified. There will be fewer landfills, and those that
do exist will be tightly controlled. There will be more incinera-
tion, more material and resource recovery, and more technological
development to destroy and detoxify wastes. Ideally, disposal
should be the procedure of last resort. However, proper disposal
will be needed even years from now. Many materials have little
recycle value, they may be too difficult to degrade, or they
contain nonflammable materials difficult to incinerate. Other
materials are residues from alternate treatment technologies.
Proper burial under RCRA will require attention to properly
engineered landfills and will require monitoring to ensure that
haz«roous waste migrates into soil or water supplies. Thus, the
analysis of hazardous waste will continue to be a vital part of
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-60
the regulation of hazardous waste. Existing methods are now being
validated and extended to handle analysis of a large number of
hazardous compounds. Also, new methods are being studies for
application to environmental analysis. Although there is a lag
time before these methods are available for application to the
analysis of hazardous waste, the reader would be well advised to
consider the merits of new methods as they have been validated and
approved for use.
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-61
References
1. Dorsey, J. A., Johnson, L.D., and Merril, R.G., "A Phased
Approach for Characterization of Multimedia Discharges from
Processes," in Monitoring Toxic Substances, D Schuetzle, ed.,
American Chemical Society, Washington, D. C., 1979.
2. Briden, F., Dorsey, J. A., and Johnson, L. D., "A Compre-
hensive Scheme for Multimedia Environmental Assessment of
Emerging Energy Technologies," Int. J_. Environ. Anal. Chem.
9:189 (1981).
3. Lentzen, D. E., Wagoner, D. E., Estes, E. D., and Outknect,
W. P., "IERL-RTP Procedures Manual: Level 1 Environmental
Assessment, 2d ed.," EPA-600/7-78-201, PB-293795, October
1978.
4. Telliard, W. A., "The Consent Decree Pollutants and Their
Analysis by GC/MS," Spectra (4):4 (1986).
5. Shackelford, W. M., and McGuire, J. M., "Analysis of Extract-
able Priority Pollutants in Water by GC/MS," Spectra 10
(4):17 (1986).
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-62
6. Federal Register. Friday, October 26, 1984, Park VIII, 43234-
43544.
7. "Test Methods for Evaluating Solid Waste, Physical/Chemical
Methods." SW-846 manual, 3d ed. Document No. 955-001-
0000001. ^Available from the Superintendent of Documents,
D. S. Government Printing Office, Washington, D. C. 20402,
January 1987.
8. Flatman, G. T., and Tfantis, A. A., "Geostatistical Strategy
for Soil Sampling: The Survey and the Census," Environ.
Monitoring Assessment 4;335 (1984).
9. 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, PB-135353, January 1980.
10. Harris, J. C., Larsen, D. J., Rechsteiner, C. E., and Thrun,
K. E., "Sampling and Analysis Methods for Hazardous Waste
Combustion," EPA-600/8-84-002, PB 84-155845. February 1984.
11. DeWees, W. G., Steinsberger, S. S., and Plaisance, S. J.,
"Hazardous Waste Treatment, Storage, and Disposal Facilities:
Field Sampling and Analysis Protocol for Collecting and
Characterizing Soil Samples from TSDF's," EPA-450/3-86-014.
October 1986.
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-63
12. Code of Federal Regulations, Title 40, Part 60, App. A,
7/1/87 edition.
13. Johnson, L. D., and Merrill, R. G., "Stack Sampling for
Organic Emissions," Toxicol. Environ. Chem. 6:109 (1983).
14. Johnson, L. D., "Detecting Waste Combustion Emissions,"
Environ. Sci. Technol. 20:223 (1986).
15. Schlickenrieder, L. N., Adams, J. W., and Thrun, K. E.,
"Modified Method S Train and Source Assessment Sampling
System Operators Manual," EPA-600/8-85-003. PB 85-169878,
February 1985.
16. Bursey, J., Hartman, J., Homolya, J., McAllister, R.,
McGaughey, J., and Wagoner, D., "Laboratory and Field Evalu-
ation of the Semi-VOST Method," Vol. I, EPA-600/4-85-075a,
PB 86-123551/AS, and Vol. II, EPA-600/4-85-075b, PB 86-
123569/AS, September 1985.
17. Margeson, J. H., Knoll, J.E., and Midgett, M. R., "An Evalu-
ation of the Seoi-VOST Method for Determining Emissions from
Hazardous Waste Incinerators," Submitted Co J. Air Pollut.
Control Assoc.
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-64
18. Bursey, J., Steger, J. L., Palazzola, M., Benson, D.,
Homolya, J., McAllister, R., HcGaughey, J., and Wagoner, 0.,
"Laboratory and Field Evaluation of the Semi-VOST Method,"
EPA-600/4-86-046, PB 87-145934/AS, November 1986.
19. Jungclaus, G. A., Gorman, P. G., Vaughn, G., Scheil, G. W.,
Bergman, F. J., Johnson, L. D., and Friedman, D. "Development
of a Volatile Organic Sampling Train (VOST)," in Proceedings,
Ninth Annual Rsearch Symposium on Land Disposal, Incinera-
tion, and Treatment of Hazardous Waste, Ft. Mitchell, KY, May
1983. PB 84-234525, July 1985.
20. Johnson, L. D., "Development of the Volatile Organic Sampling
Train for Use in Determining .Incinerator Efficiency,"
Hazardous and Industrial Solid Waste Testing: Fourth
Symposium, ASTM STP 886, J. K. Petros, Jr., W. J. Lacy, and
R. A. Gonway, eds., American Society for Testing and
Materials, Philadelphia, 1986, pp. 335-343.
21. Hansen, E. M., "Protocol for the Collection and Analysis of
Volatile POHC's Using VOST," EPA-600/8-84-007, PB 84-170042,
March 1984.
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Samplinp and Analysis of Hazardous Wastes
8-65
22. ?rohaska, J., Logan, T. J., Fuerst, R. G., and Midgett,
N. R., "Validation of the Volatile Organic Sampling Train
(VOST) Protocol," Vol. I, "Laboratory Phases," Vol. II, "Field
Validation Phase," EPA-600/4-86-014a, PB 86-14:547, and
EPA-600/4-86-014b, PB 86-145554, January 1986.
23. Fuerst, R. G., Logan, T. J., Midgett, M. R., and
Prohaska, J., "Validation Studies of the Protocol for the
Volatile Organic Sampling Train/' £. Air Pollut. Control
Aasoc. 37 (4):388 (1987).
24. Thrun, K. £., Harris, J. C., Beltis, K., "Gas Sample
Storage," EPA-600/7-79-095, PB 298-350, April 1979.
25. Beltis, K. J., DeMarco, A. J., Grady, V. A., and Harris,
J. C., "Stack Sampling and Analysis of Formaldehyde," in
Proceedings, Ninth Annual Research Symposium on Land
Disposal, Incineration, and Treatment £f Hazardous Waste,
Ft. Mitchell, KY, May 1983, EPA-600/9-84-015, PB 84-234525,
July 1984.
26. U. S. Environmental Protection Agency, "Methods for Chemical
Analysis of Waste and Waste," EPA-600/4-79-020, March 1979.
-------
Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
d-66
27. U.S. Environmental Protection Agency, "Handbook for Sampling
and Sample Preservation of Water and Wastewater," EPA-600/4-
82-029, September 1982.
28. Jayanty, R. K. M., Sokash, J. A., Outknecht, W. P., Decker,
C. E., and Von Lehmden, D. J., "Quality Assurance for
Principal Organic Hazardous Constituents (POHC) Measurements
During Hazardous Waste Trial Burn Tests," ^J. Air Pollut.
Control Assoc. 35 (2):143 (1985).
29. Jayanty, R .K. M., Cooper, S. W., Decker, C. E., and von
Lehmden, D. J., "Evaluation of Parts-Per-Billion Organic
Cylinder Gases for Use as Audits During Hazardous Waste Trial
Burn Tests," £. Air Pollut. Control Assoc. 35 (11):1195
(1985).
30. Lee, C. C., Huffman, G. L., and Oberacker, D. A.,
"Hazardous/Toxic Waste Incineration," J_. Air Pollut. Control
Assoc. 36 (8):922 (1986).
31. Sweet, W. E., Ross, R. D., and Vander Velde, G. "Hazardous
Waste Incineration: A Progress Report," J_. Air Pollut.
Control Assoc. 35 (2):139 (1985).
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Larry D. Johnson
Std KB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-67
32. Oppelt, E. T., "Hazardous Waste Destruction," Environ. Sci.
Teehnol. 20 (4):312 (1986).
33. Comprehensive Environmental Response, Compensation, and
Liability Act, (42 USC 9601-9657, Section 101 (42 USC 9601),
1980.
34. McNair H. M., "Analytical Systems for Trace Organic
Analyses," National Bureau of Standards Special Publication
519, Proceedings £f_ the 9th Materials Research Symposium,
April 10-13, 1978, Gaithersburg, MO, (issued April 1979).
35.
36. Keith, L. H., Crummett, W., Deegan, J., Jr., Libby, R. A.,
Taylor. J. K., and Wentler, G., "Principles of Environmental
Analysis," Anal. Chem. 55 (14):2210 (1983).
37. Johnson, J. H., Erickson, E. D., and Smith, S. R., "Artifacts
Observed When Using Tenax-GC for Gas Sampling," Anal. Lett.
19 (3 & 4):315 (1986).
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-68
38. Daisey, J.M., Chemey, J.L., and Leoy, P.J. Profiles of
Organic Particulate Emissions from Air Pollution Sources:
Status and Needs for Receptor Source Appointment Modeling.
39. Weston, A. F., "Obtaining Reliable Priority-Pollutant
Analyses," Chem. Eng. April 30, 1984.
40. James, R. H., Adams, R. E., Finkel, J. M., Miller, H. C., and
Johnson, L. D., "Evaluation of Analytical Methods for the
Determination of POHC in Combustion Products," J_. Air Pollut.
Control Assoc. 35 (9):959 (1985).
41. Castaidini, C., et al, Field Tests of Industrial Boilers
Cofiring Hazardous Wastes. Hazardous Waste. 1:159, 1984.
42. Shaub, W. M. and Tsang, W., "Dioxin Formation in Incinera-
tors," Environ. Sci. Technol. 17 (12):721 (1983).
43. Group C-Environmental Standards Workshop. Analytical Proce-
dures to Assay Stack Efflrent Samples and Residual Combustion
Products for Polychlorinated Dibenzo-j>-Dioxins (PCDD) and
Polychlorinated Dibenzofurans (PCDF). Sponsored by The
American Society of Mechanical Engineers, U.S. Department of
Energy, and U.S. Environmental Protection Agency, September
18, 1984.
to?
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Larry D. Johnson
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
8-69
44. Rappe, C., "Analysis of Polychlorinated Oioxins and Furans,"
Environ. Sci. Techno!. 18 (3):78A (1984).
45. Dallinger, B., and Hall, D. L., "Surrogate Compounds, for
Monitoring the Effectiveness of Incineration Systems,"
J. Air Pol1 «it. Control Assoc. 32 (2):179 February (1986).
46. Dellinger, B., and Hall, D. L., "The Viability of Using
Surrogate Compounds for Monitoring the Effectiveness of
Incineration Systems," £. Air Pollut. Control Assoc. 36
(2):179 (1986).
47. Almich, B. P., Budde, W. L., and Shobe, W. R., "Waste
Monitoring," Environ. Sci. Techno!. 20 (1):16 (1986).
48. Quality Assurance Management Staff, Office of Research
Development, "Guidelines and Specifications for Preparing
Quality Assurance Program Plans," U.S. EPA, Washington, D.C.,
QAMS-004/80; EPA-600/8-83-024, PB 83-219667, September 1980.
49. Quality Assurance Management Stuff, Office of Research
Development, "Interim Guidelines and Specifications for
Preparing Quality Assurance Project Plans," U.S. EPA
Washington, D.C., QAMS-005/80; EPA-600/4-83-004, PB 83-
170514, December 1980.
-------
Table 8.1 Examples of Sampling Equipment fur Particular Waste Types
-l
Waste type
Free-flowing
liquids and
slurries
Sludges
Moist powders
or granules
Dry powders
or granules
Sand or packed
powders and
granules
Drum
Coliwasa
Trier
Trier
Thief
Auger
Sacks
and
bags
N/A
N/A
Trier
Thief
Auger
Open-
bed
truck
N/A
Trier
Trier
Thief
Auger
Waste
Closed-
bed
truck
Coliwasa
Trier r
Trier
Thief
Auger
location or container
Storage
tanks
or bins
Weighted
bottle
Trier
Trier
*
Thief
Pond s ,
Waste lagoons, Conveyor
piles pits belt
N/A Dipper N/A
* *
Trier Trier Shovel
Thief Thief Shovel
Thief * Dipper
Pipe
Dipper
Dipper
Dipper
Dipper
K •
00
•
Sampling
a>
9
O.
£
B>
u»
«
0
Mt
?
S
3.
0
S
f
rr
(•
rr
0.
g?
N
>"l
O
ifl
f
rr
"
H
(D
rr
r»
rr
0>
£?.
•O
o
5"
X
0
•
9
w
0
9
solids
trier trier trier trier trier trier trier
*This type of sampling situation can present significant logistical sampling problems, and
sampling equipment must be specifically selected or designed based on site and waste condi-
tions. No general statement about appropriate sampling equipment can be made.
SOURCE: This table reproduced from "Test Methods for Evaluating Solid Waste, Physical/
Chemical Methods." SW-846 Manual, 3d ed. Document No. 955-001-0000001. Avail-
able from the Superintendent of Documents, U.S. Government Printing Office,
Washington, D.C., January 1987.
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Larry D. Johnson
Std KB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.2 Techniques for Trace Organic Analysis
Technique
GC
LC
MS
Detector
Thermal conductivity
Flame ionization
Electron capture
Nitrogen phosphorus
(nitrogen mode)
Nitrogen phosphorus
(phosphorus mode)
Flame photometric
(sulphur mode)
Flame photometric
(phosphorus mode)
Hall electrolytic
conductivity
Pho to ion i zat ion
Ultraviolet/visible
Electrochemical
Fluorescence
Total ion current
Selected ion monitoring
Estimated
sensitivity,
g
lO-'
10-"
10-13
lO-"
10-"
10-9
10-1 1
10-"
10-11
10-9
10-10
10-12
10-9
10-12
Selectivity
universal
universal
selective
selective
selective
selective
selective
selective
selective
universal
selective
selective
universal
selective
NOTE: GC • gas chromatography, LC • liquid chromatography,
MS • mass spectrometry.
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Ruby H. James
Std KB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis 2 Hazardous Wastes
Table 8.3 Test Methods for Evaluation of Solid Wastes
Physical/Chemical Methods SW 846
Procedure
SW 806
method no.
Procedure
SW846
method no.
Waste Evaluation Procedures
IgaitabiUty 1010:1020
Corrosivity 1110
Electrochemical Corrosion Method 1120
Extraction Procedure Toxicity 1310
Multiple Extraction Procedure 1320
Sample Workup Techniques
Acid Digestion mxedure for Plane
Atomic Absorption Spectroscopy 3010
Acid Digestion procedure for Furnace
Atomic Absorption Spectrosccpy 3020
Acid Digestion of Oils, Greases
or Waxes 3030
Digestion Procedure for Oils,
Greases or Vfaxes 3040
Acid Digestion of Sludges 3050
Alkaline Digestion 3060
Separately Funnel Liquid-Liquid
Extraction 3510
Continuous Liquid-Liquid Extraction 3520
Acid-Sase Cleanup Extraction 3530
Soxhlet Extraction 3540
Sonication Extraction 3550
Reverse Phase Cartridge Extraction 3560
Cblum Cleanup of Petroleun Waste 3570
Protocol for Analysis of Sbrbent
Cartridge from Volatils Organic
Sampling Drain 3720
Sample Introduction Techniques
leadspace 5020
Purge and Trap 5030
Mtiltielanental Inorganic Analytical
Methods
Inductively Coupled Plaana Method
Analytical Methods
:ion)
ariati
)
:unony UA, Direct te
(AA, Graphite Furnace!
Arsenic (AA, Furnace)
(AA, Gaseous Hydride)
Bariu* (AA, Direct Aspiration)
(AA, Furnace)
Beryl liun (AA, Direct Aspiration)
{AA, Furnace)
6010
7040
7041
7060
7061
7080
7081
7090
7091
Cadmiun (AA, Direct Aspiration) 7130
(AA, Furnace) 7131
Chroniun (AA, Direct Aspiration)
(AA, Furnace) 7191
Hsxavalent Chroniun: Cbprecipitation 7195
Hexavalent Chroniun: Color metric 7196
Hsxavalent Chroniun: Chelation-
'.wtraction 7197
Hexavalent Chroniun: Differential
Pulse Pblarography 7198
Copper (AA, Direct Aspiration) 7210
(AA, Furnace) 7211
Iron (AA, Direct Aspiration) 7380
(AA, Furnace) 7381
Manganese (AA, Direct Aspiration) 7460
(AA, Furnace) 7461
Mercury
Mercury in Liquid Waste (Manual
Cold-Vapor Technique) 7470
Mercury in Solid or Saoisolid
Waste (Manual Cold-Vapor
Technique) 7471
Nickel (AA, Direct Aspiration) 7520
(AA, Furnace) 7551
Oaniun (AA, Direct Aspiration) 7550
(AA, Furnace) 7551
Selenium (AA, Furnace) 7740
(A*. Caseous Hydride) 7741
Silver (AA, Direct Aspiration) 7760
(AA, Furnace) 7761
Sod inn (AA, Direct Aspiration) 7840
(AA, Furnace) 7841
Vanadiun (AA, Direct Aspiration) 7910
(AA, Furnace) 7911
Zinc (AA, Direct Aspiration) 7950
(AA, Furnace) 7951
Analytical Methods
Organic
57 M
recnoos
Haiogenatad Volatile Organic a 8010
fenhalogenated Vblatile Organ its 8015
Aromatic Vblatile Organic! 8020
Acrolein, Acrylonitriie,
Acetonitrile 8030
(continued)
-------
Ruby H. James
Std HB Cor Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.3 Test Methods for Evaluation of Solid Wastes
Physical/Chemical Methods SW 846
(continued)
Procedure
SW846
method no.
Procedure
SI 846
method no.
Analytical Methods
~m£hods icont uiuedj
Phenols 8040
Rithalate Esters 8060
Organochlorine Pestkides and PCBs 8080
Nitroaraaatics and Cyclic fe tones 8090
Polynuclear Aromatk Hydrocarbons 8120
Organophosphorus ftestkides 8140
Chlorinated Herbkides 8150
OC/MS Methods
GC/MS Method for Volatile Organks 8240
GC/MS Method for Sanivolatile
Organks:
Packed Column Technique 8250
Capillary Coluna Technique 8270
HPIC Methods
Polynuclear Aromatk Hydrocarbons 8310
Miscellaneous Compounds 8320
Thioureas and Other Compounds 8330
formaldehyde: Bask Mediun 8410
Formaldehyde: Acidic Median 8411
ffierarchkal Analytical Protocol
for GroundwBter 8600
Total Arcmatics by Ultraviolet
Absorption 8610
Total Nitrogen-Phosphorus Gas
Gnromatographable Compounds 8620
Derivatization Procedure for
Appendix VIII Compounds 8630
Miscellaneous Analytical Methods
local and Aaerat'le Lyanifle 9010
Method for the Deterainatkn of
PhotDdegradable Cyanides 9011
Total Organk Hal ides (TDK) by
Mkrocoulcmetric Titration 9020
Total Organk Hal ides (TOK) by
Neutron Activation Analysis 9022
Sulfides 9030
Sulfate (Cblorimetrk, Automated,
Chloranilate) 9035
(ColorimeCric, Automated,
Methylthyool Blue, AA II) 9036
(Gravimetric) 9037
(Turbidimetrk) 9038
pH Measuranent 9040
Paper Method 9041
Soil pH 9045
Specifk Conductance 9050
Total Organk Carbon 9060
Phenolks (Spectrophotcmetric,
Manual 4-AAP with Distillation) 9065
(Cblorimetrk, Automated 4-AAP
with Distillation) 9066
(Specrrophotanetrk, MBTH with
Distillation) 9067
Oil and Grease, total Recoverable
(Qravimetrk, SeparatDty Funnel
detraction 9070
Extraction Method for Sludge Sanples 9071
Cation Exchange Capacity
(Amoniun Acetate) 9CSO
(Sodiun Acetate) 9081
Conpatibility Test for Wastes and
Maabrane Liners 9090
Saturated Hydraulk Conductivity,
Saturated leachate Conductivity
and Intrinsk fenneability Methods 9100
Tbtal Coliform: Multiple Tube
fc meat ion Technique 9131
Manbrane Filter Technique 9132
Nitrate 9200
Chloride (Cblorimetrk, ^qMtefl
Ferrkyanide AA 0 9250
(Cblorimetrk, Automated
Ferrkyanide AA II) 9251
(Titrimetrk, Mercurk Nitrate) 9252
Grease Alpha and Grease Beta 9310
Alpha-Quitting Radium Isotopes 9313
RadiuD-228 9320
-------
Ruby H. James
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.4 Sampling and Analysis Method for
Hazardous Waste Combustion
Procedure Method No.
SAMPLE PREPARATION:
Representative Aliquots from Field Samples
--Liquids (Aqueous and Organic) P001
—Sludges P002
—Solids P003
Solvent Extraction of Organic Compounds
—Aqueous Liquids P021
—Sludges P022
—Organic Liquids P023
—Solids P024
Drying and Concentrating of Solvent Extracts P031
Digestion Procedures for Metals P032
Sample Cleanup Procedures
—Florisil P041
—Biobeads SC-3 P042
—Silica Gel P043
—Alumina P044
—Liquid/Liquid Extraction P045
ANALYSIS:
Ignitability C001
Corrosivity C002
Reactivity C003
Extraction Procedure Toxicity C004
Moisture, Solid, and Ash Content A001-A002
Elemental Composition A003
Total Organic Halogens A004
Viscosity A005
Heating Value of the Waste A006
Survey Analysis of Organic Content
—Total Chromatographable Organics A011
—Gravimetric Value A012
—Volatiles A013
—Infrared A014
—Mass Spectrometric A015
—CC/MS A016
—HPLC/IR or HPLC A017
(continued)
-------
Ruby H. Janes
Sed HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.4 Sampling and Analysis Method for
Hazardous Waste Combustion
(continued)
Procedure Method No.
AHALTSIS:
(continued)
Survey Analysis of Inorganics
Analytical Methods
—Volatiles A101
—VOST A102
—Extractables A121
—HPLC/UV A122-A124
--HPLC/Fluorescence A12S
—Aldehydes/Ketones A131
—Carboxylic Acids A133
—Oxiraes A183
—-Organometallics A191
—Metals A211-A24S
—Anions A2S2-A2S4; A256
—Gases A141
SOURCE: J.C. Harris, D.J. Larsen, C.E. Rechsteiner, and R.E.
Thrun, "Sampling and Analysis Methods for Hazardous
Waste Combustion." EPA-600/8-84-002, PB 84-155845,
February 1984.
-------
Ruby H. James
Scd HB fur Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.S. EPA Toxicity Threshold Levels
Contaminant
Herbicides
2,4-D
2.4,5-TP
Metals
Arsenic
Barium
Cadmium
Chromium (VI)
Lead
Mercury
Selenium
Silver
Pesticides
End r in
Lindane
Methoxychlor
Toxaphene
Threshold level,
ng/L
10.0
1.0
5.0
100.0
1.0
S.O
5.0
0.2
1.0
S.O
0.02
0.4
10.0
0.5
-------
Ruby H. James
Std HB Cor Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.6 Toxicity Characteristic Contaminants
and Regulatory Levels
Regulatory level,
Contaminant . mg/L
Acrylonitrile 5.0
Arsenic S.O
Bariun 100
Benzene 0.07
Bis(2-chloroethyl) ether 0.05
Cadmium 1.0
Carbon disulfide 14.4
Carbon tetrachloride 0.07
Chlordane 0.03
Chlorobenzene 1.4
Chloroform 0.07
Chromium 5.0
o-Cresol 10.0
m-Cresol 10.0
p-Cresol 10.0
2,4-D 1.4
1,2-Dichlorobenzene 4.3
1,4-Dichlorobenzene 10.8
1,2-Dichloroethane 0.40
1,1-Dichloroethylene 0.1
2,4-Dinitrotoluene 0.13
Endrin 0.003
Heptachlor 0.001
Hexachlorobenzene 0.13
Hexachlorobutadiene 0.72
Hexachloroethane 4.3
Isobutanol 36
Lead 5.0
Lindane 0.06
Mercury 0.2
Methoxychlor 1.4
Methylene chloride 8.6
Methyl ethyl ketone 7.2
Nitrobenzene 0.13
Pentachlorophenol 3.6
Phenol 14.4
Pyridine .S.O
(continued)
-------
Ruby H. James
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Tabl« 8.6 Toxicity Characteristic Contaminants
and Regulatory Levels
(continued)
Regulatory level ,
Contaminant tng/L
Selenium 1.0
Silver 5.0
1,1,1,2-Tetrachloroethane 10.0
1,1,2,2-Tetrachloroethane 1.3
Tetrachloroethylene 0.1
2,3,4,6-Tetrachlorophenol 1.5
Toluene 14.4
Toxaphene 0.07
1,1,1-Trichloroethane 30
1,1,2-Trichloroethaoe 1.2
Trichloroethylene 0.07
2,4,5-Trichlorophenol 5.8
2,4,6-Trichlorophcnol 0.30
2,4,5-TP (Silvex) 0.14
Vinyl chloride 0.05
-------
Ruby H. James
S;d HB for Hazardous Waste Treatment i Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.7 Land Disposal Constituents
Concentration,
Hazardous constituent rag/L
Acetone 2.0
j»-Butyl alcohol 2.0
Ca-boo disulfide 2.0
Carbon tetrachloride 0.1
Chlorobenzene 2.0
Cresuls 2.0
-ycIohexanone 2.0
E-.hylene acetate 2.0
Ethylene benzene 2.0
Ethyl ether 2.0
HxCLD-All Hexachlorodibenzo-j>-dioxins 0.001
HxCDF-All Hexachlorodibenzofurans 0.001
Isobutano! 2.0
Hethanol 2.0
Methylene chloride 1.2
Methyl ethyl ketone 2.0
Methyl isobutyl ketone 2.0
Nitrobenzene 0.09
DeCDD-\ll Pentachlorodibenzo-£-dioxins 0.001
PeCDF-All Pentachlorodibenzofurans 0.001
Penta-jhlorophenol 1.0
Pyridine 0.7
TCI>D-All Tetrachlorodibenzo-^-dioxins 0.001
TCDF-All Tetrachlorodibrnzofurans 0.001
Tetrachloroethylene 0.015
2,3,4,6-Tetrachlorophenol 2.0
Toluene 2.0
1,1,1 -Trichloroethane 2.0
l,7,2-Trichloro-l,2,2-crifluoroethane 2.0
Tricnloroethylene 0.1
Trie: lorof 1'joromechane 2.0
*.,4,3-7»icblcrophenol 8.0
2,4,6-Trichlorophenol O.C*
Xylene 2.C
-------
Ruby H. James
Std KB for Hazardous Waste Treatmenr & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.8 Methods for Chemical Analyses of Water and Wastes
EPA
reference
method
Priority pollutants
Method of analysis
601
602
603
604
60S
606
607
608
609
Purgeabie halocarbons
Purgeable aromatics
Acrolein and Acrylo-
nitrile
Phenols
Benzidines
Phthalate esters
Nitrosamines
Organochlorine
pesticides and PCBs
Nitroaronatics and
isophorone
Purge-and-trap (PAT), GC,
detection with a Hall (elec-
trolytic) detector
PAT, GC, photoionirat ion
detector
PAT, GC flame ionization
detector
Extraction, Kuderna-Danish
(KD) concentration GC, flame
ionization-electron capture
detection
Extraction, concentration,
HPLC, electrochemical detec-
tion
Extraction, Florisil or
alumina cleanup KD concentra-
tion, GC, flame ionization-
capture detection
Extraction, Florisil or
alumina cleanup KD conceritta-
tion, GC, flame ionization-
electron Capture detection
Extraction, Florisil or
alumina cleanup, KD concentra-
tion, GC, detection
Extraction, KD concentration,
GC, flame ionization-electron
capture detection
(continued)
-------
Ruby H. James
Scd HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.8 Methods for Chemical Analyses of Water and Wastes
(continued)
EPA
reference
method
Priority pollutants
Method of analysis
610
611
612
613
624
625
Pol/nuclear aromatic
hydrocarbons
Haloethers
Chlorinated hydrocarbons
2,3,7,8-Tetrachlorodi-
benzo-j>-diox.in
Volatile organic
comopunds (purgeable)
Semivolatile Organic
compounds (base neutral
and acid extractable
compounds)
Extraction, KD concentration,
GC, tlame ionization detection
or HPLC UV fluorescence detec-
tion
Extraction, solvent exchange,
KD concentration, GC, electron
capture detection
Extraction, solvent exchange,
KD concentration, GC, electron
capture detection
Spiking with labeled 2,3,7,8-
TCDD, extraction, solvent
exchange, KD concentration,
analysis by GC/MS
PAT analysis by GC/MS
Extraction, KD concentration,
analysis by GC/MS
-------
Table 8.9 Listing uf Tuxic Organic*
Gomun none
Priority Super fund Appendix
fellutanC list DC
Comun
Priority Super fund Appendix
pollutant line IX
Organic!
acenai'hthene
acenaphthylene
acetone
acetunitrile
acctophenone
2-acetylaninofluDrene
acrolein
acrylonitrile
eldrin
allyl alcohol
4-oninobiphenyl
aniline
anthracene
aranite
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aruclor 1254
Arxlor 1260
benzene
benzene thiol
benzidine
benzo( a)anthracene
benzo(b)f 1uoranthene
benzo( k) fl uoranthene
benzoic acid
benzo(a)pyrene
benzo( )pyrene
jr-benaxftinone
X
• t
A
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X X benzyl alcohol
X X alpha-fiHC X
X X* beta-BHC X
X delta-BHC X
X ganna-BHC X
X bis(2-chloroethoxy)nethane X
X bis(2-vhloroethyl tetter X
X bis(2-chloroiu>propyl)ether X
X X bis(2-ethylhexyl)phthalate X
X brunodichlorunethane X
X brunonethane X
X 4-bronophenyl phenyl ether X
X X butyl benzyl phthalate X
X 2-sec-butyl-4,6-dinitrophenbl
X X carbon disulfide
X X carbon tetrachloridc X
X X chiordane X
X X p-chloroanil ine
X X chlorobenzene X
X X chlorobenzilate
X X 2-chloro-l,3-butadiene
X X p-chloro-nrcresol X
X chlorod ibraomethane X
X chloroethane X
X X 2-vhloroethyl vinyl ether X
X X chloroform X
X X chloronethane X
X X* 2-chloronaphthalene X
X X 2-xhlorophenol X
X X 4-chlorophsnyl phenyl ether X
X 3-chloropropene
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
rt
a
*- c
ft
3
Q.
»
N
»
O
C
§
IP
«< c
w ft
f- at
91 r*
It
O
rn H
? :
S 3
i n
& 3
O rt
ce 0<
ft= ?-
CD «
rr TB
A O
u> <•
ft
(continued)
-------
Table 8.9 Listing of Tbxit Organic*
(continued)
Cannon none
Priority Superfund Appendix
Pollutant I tat IX
Gnroun none
Priority Suoerfund Appendix
pollutant list IX
Organic* (continued)
3-Chl crop-opium trite
chrysene
ortho-cresol
pera-xreaol
4,4'-DDO
4.4MXC
4.4I-ODT
d ibenau( a ,h)anthraKRne
d ihenaif uran
a ibenau( a ,«) pyrene
d ibenzo(a ,h)pyrene
d ibenzo( a , i ) pyrene
l,2"dibrono-3-vhloro-
propane
1 ,2-d ibr onanethane
dibronunethane
di-tHxityl phthalate
nrdjchlorobenzene
£tl ichlorobenaene
£-d\chlarobeniene
3,3 ' -d ichlorobenzid ins
trans-1.4-dit:hlcro-2-
butenu
d ichlorod i f 1 uuruneChane
1 1 1-d icliloroethane
1 , 2-d ichloroethone
1 , 1-d ichloroethy lene
trana-l ,2-dkhlaroethylene
d ichluranethane
2 ,4-d ic hlorophenol
2,6-dichlorjphsnol
2,4-dichlaropt>muxy-
aL-etk acid
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
A
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
wr
A
1 ,2-d ichloropropane
cis-1 ,3-dichloropropene
trans-1 ,3-dichloropropene
dieldrin
diethyl phthalate
0,0-diethyl-0,2-pyrazinyl
phuepluroth ioate
3,3 '-d iioethdxybenzid ine
j>-d imethyl aninoaaibenaene
7~,12-diaethylbenz(a)-
anthracene
3, 3'-dimethylbenzidine
alpha, alpha-dunethyl-
pnenethylanine
2 ,4-d imethyl phenol
dimethyl phthalate
m-dinitrobenaene
7,6-tJinitro^pjxresol
2,4-dini trophenol
2,4-ditiitrotoluene
2,6^dinitrotoluene
di-n-octyl phthalate
1,4-dioxane
diphenylanine
1,2-diphenylhydrazine
di-n-propylnitrosanine
dislfotxxi
endosul£an sulCate
endusulfan I (alpha)
endosulCan 11 (beta)
endrin
end r in aldehyde
endrin ketxxte
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
(continued)
J? ff
o. er
M
•O m
r- C
I
n
u
O.
c
M PI
K. (0
w rr
C
Hi *^
1
g? 2
S a
i »
g- 3
e
» tr>
C o
• »
fT ^J
fll O
(O <•
fii
-------
Table 8.9 Listing of tacit- Organic*
(continued)
Canaan none
Priority Superfund Appendix
Pollutant Use U
Gxnun none
Priority Superfund Appendix
pollutant list IX
Organic* (continued)
ethyl benzene
ethyl cyanide
ethylena oxide
ethyl aeehacrylate
fanphur
fluuranthene
fluorene
heptachior
heptachlor epvide
hexachlorooenzene
hexachlorobutadiene
hexachlorocyc lopentad iene
nexachlorud ibenzu-£-
dioxina
hexachlorod iben*>f urans
hexau hi oroe thane
hexauhlorophene
hncachlnropropene
2-heunune
indeno(1.2»3-cd)pyrene
iodoaethane
isobutyl alcohol
iaodrin
iao^urone
iaosafirole
kepone
malononitrile
methacryloniCrile
•etitapyrilene
•erhux^chlor
>v?thylcholanthrer«
X
X
X
X
X
X
X
chloroaniline)
X X* methyl ethyl ketune
X methyl nethylacrylate
X methyl oechanesul funate
X 2-nethylnaphthalene
X methyl parathion
X X 4-meehyl-2-pentanone
X X 2-nethyl phenol
X X Arnethylphenol
X X naphthalene X
X X l,
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
OB CO 50
rt C
o. cr
M X **
g - F
•O rn
— C k«
I " s
* ? 5
» N
3 ft
a. t
a.
> c
» CD
rr
n
n
a: <•
to »
S a
1 5
O r»
(continued)
-------
Table 8.9 Listing of Italic Organic*
(continued)
Gmun none
Priority Superfund Appendix
fellutant list IX
Graun name
friurity Superfund Appendix
pollutant list IX
Organic* (continued)
pentachloroni brobenzene
pentau hi orophenol
phenaL-etine
pher^nChrette
phenol
phorate
2-picoline
prunaraide
2-propyn-l-ol
pyrene
pyridine
rescrcinol
safrjle
silvex
styrene
2.4,5-T
1 ,2,4,5-tetrachlorcbeni
2 , 3, 7,fr-tetracnlarud ibenao-
X
X
tetrachlurodibenar-p-dioxina
tetrachlorod ibennfurans
1,1,1 ,2-tetrachloroethane
X 1,1,2,2-tetraL-hloroethane X
X X tetraL-hloroechylene X
X 2,3,4,6-tetrathlorophenol
X X tetraethyldithiopyro-
X X phosphate
X toluene X
X toxaptene X
X tribromunethaiw X
X l,2,4-trii;hlorobenaene X
X X 1,1,1-trichlaroeChane X
X 1,1,2-tr k-hloroethane X
X trichloroethylene X
X trkhlorunethanethiol
X trkhluroDunofluoro-
X Xa methane
X 2,4,S-trk.hloiophenol
X 2.4,&-trkhlorophenol X
1,2,3-tr k-hloropropane
X tris(2,3-dibraa>propyl)
X phosphate
X vinyl acetate
X vinyl chloride X
total xylenes
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Jp
00 C/J
I '
"9 «.
»- c
3 »
O. »|
? I
ft oe
R
i? 2
S a
3. 2
O rt
C
a
r»
ec
rr
19
-o
O
•Added fron Superfund list.
-------
Ruby H. James
Std HB for Hazardous Waste Treatment & Disposal
8. Saopi ing and Analysis of Hazardous Wastes
Table 8.10 Toxic Inorganic Substances
Common naraa
Metals
aluminum
antimony
arsenic
barium
beryllium
cadmium
calcium
chromium
cobalt
copper
iron
lead
magnesium
manganese
mercury
nickel
osmium
potassium
selenium
silver
sodium
thallium
tin
vanadium
zinv
Miscellaneous
cyanide
f luoi ide
phenols
sulfide
Priority
pollutant
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Append ix
IXa
Xb
X
X
X
X
X
Xb
X
Xb
X
xb
X
Xb
xb
X
X
X
xb
X
X
Xb
Xb
xb
X
X
X
X
X
Super fund
list
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
^Derived from Appendix VIII.
b Added from Super fund List.
-------
Ruby H. James
Std HB for Hazardous Waste Treatment & Disposal
8. Samp I i tig and Analysis of Hazardous Wastes
Table 8.11 Recommended (AAS) Analysis Methods
Element
Ag
As
Ba
Be
Gd
Cr
Cu
Ug
Hi
Os
Pb
SW 846
method no .
7760
7761
7060
7061
7080
7081
7090
70S1
7130
7131
7190
7191
7195
7196
7197
7198
7120
7121
7470
7 520
7521
7550
7551
7420
7421
Description
Direct aspiration
Graphite furnace
Graphite furnace
Gaseous hydride method
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
Hexavalent Cr: Coprecipitaeion
Hexavalent Cr: Colorimetric
Hexavalent Cr: Che 1 at ion-Extract ion
Hexavalent Cr: Differential Pulse
Polarography
Direct aspiration
Graphite furnace
Hg in liquid waste
(Manual cold vapor technique)
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
(continued)
-------
Ruby H. James
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.11 Recommended (AAS) Analysis Methods
(continued)
Element
Sb
Ti
V
Zn
SW 846
method no.
7040
7041
7840
7841
7910
7911
7950
7951
Description
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
Direct aspiration
Graphite furnace
-------
Ruby H. James
Std HB for Hazardous Waste Treatment & Disposal
8. Sampling and Analysis of Hazardous Wastes
Table 8.12 Experimentally Observed PICs
Parent
(POHC)
Product
(PIC/POHC)
Chloroform
Carbon tetrachloride
Toluene
Chlorobenzene
Trichlorobenzene
Pentachloroethane
Polychlorinated biphenyls
Polychlorianted phenols
Kepone
letrachloroethylene
Carbon tetrachloride
Tetrachloroethylene
Hexachloroethane
Benzene
Benzene
Dichlorobenzene
Chlorobenzene
Tetrachloroethylene
Chlorinated dibenzofurans
Chlorinated dibenzodioxins
Hexachlorobenzene
-------
}M(«|1 i/t i
-------
Nut
Figure 8-2. Weighted bottle sampler.
-------
VtrifripChmp
Tttncoptaf AhimUwjm .'
2.5 lo 4.S Mclm (6 to IS N J
150
Figure 8-3. Dipper
-------
60-100 em
-HH-
1.27-23* cm
Figure 8-4. Thief sampler.
-------
122-183 em
<48-72"»
6.08-7.62 cm
\
60-100 cm
N
1.27-2.S4 em
Figure 8-5. Sampling triers,
-------
ItoUtlon
BaNValvt
Condom*!*
Coltoclor
thy GM Mtttr^Mfk* Mt«w
•nd Pionurt Rtadoul
Control Modwlt
T.C.
«*• KM t'/mln 1780 L/mJn)
—Vacuum Pump*
Figure 8-6. Source assessment sampling system (SASS).
-------
Ttmp«ratuf«
S«iuor
RtcircuUtion Pump
Thermo mctwi
VMMMlUlM
Dry Cat Air light
Mtttr
Figure 8-7. Modified Method 5 train.
-------
HtotrtProb*
Clots Wool
Porticulolt
Fill*
Uolotion Volwt
Filltf
Thtrmocouplo
Sorbent
Cartridge
ffl
Condensrlt
Trap
CondtfiMr
Backup
Sorb«nt
Cortridgt
Silica Gtl
Vacuum
Indicator
.Exhaust
Dry Cot
Mtftr
Rofomtttr
Figure 8-8. Volatile organic sampling train (VOST).
-------
CHARACTERISTICS
—Ignitability
—Corroaivity
—•Reactivity
—Toxic ity (BP Test)
COMPOSITE WASTE SAMPLE
PROXIMATE ANALYSIS
Physical Pon and
Approximate Maas Balance:
—Moiature (Volatile)
Content
—Solid Content
~Aah Content
—Elemental Analyaia
•-Heating Value of
the Waate
—Viacoaity
(Physical Porn)
COMPOSITION
SURVEY ANALYSIS
DIRECTED ANALYSIS
Overall Description of
Sample With Estimated
Quantitlea of Major
Componenta:
—Total Organic Content
-—Organic Compound
Classes
—Specific Major
Organic Componenta
—Specific Major
Inorganic Elements
Identification and
Quantification of
the Hazardous Con-
stituents Selected
from the Appendix
VIII Liat
Figure 8-9. Overview of the analytical approach for waste characterisation.
-------
H6
vosr
Probe fesh
Paniculate Citch
flbrbent Trap
Qmcentrate Co
tryness
P" *** I [
Cbabine filtrates
Aliquot («UK)
by 1CAP
(If any Metals
Sadilet Btcraccion
Qmucntrate*
%ecific Aialyala
(OC/MS)
*A. aa altanatfo, cha
Cbndeneata
Snhlet Bttractlun
Uquid/Li<|iid
Bccraecion
Cbnbine Ektracet
Qmcentrace*
$e
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