FIELD INVESTIGATIONS OF
UNCONTROLLED HAZARDOUS WASTE SITES
FIT PROJECT
TASK REPORT TO THE
ENVIRONMENTAL PROTECTION AGENCY
CONTRACT NO. 68-01-6056
DRAFT
INTERIM REPORT
ON A
PROTOCOL FOR FIELD CHARACTERIZATION
OF HAZARDOUS WASTE
3 August, 1981
Prepared by: David Jackson
TDD No. F-7-8103-4A
ecology and environment, inc.
International Specialists in the Environmental Sciences
063100
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TABLE OF CONTENTS
Page
SECTION 1: INTRODUCTION 1
SECTION 2: SAFETY 2
SECTION 3: DOCUMENTATION 3
SECTION 4: PROCEDURE 4
Site Entry and Safety Characterization 5
General Visual Checks and Physical Characteristics ... 6
Sample Acquisition 6
General Liquid Characterization 7
Inorganic Liquid Characterization 8
Organic Liquid Characterization 11
Solids Characterization 12
SECTION 5: CONDENSED PROCEDURE FOR FIELD CHARACTERIZATION
OF HAZARDOUS WASTE 14
SECTION 6: CONCLUSION 17
REFERENCES . . 19
ACKNOWLEDGEMENTS 19
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SECTION 1: INTRODUCTION
This report provides consecutive methods for field characterization
of hazardous waste. It is predicated on the assumption that initially
nothing is known about the waste at a site. Obviously, this will not
always be the case. There will sometimes be much available information
on the history of a site and the wastes which have been disposed there.
It is very important to exhaust all background information resources
and complete off-site reconnaissance before an attempt is made to enter a
site and begin waste characterization.
The scheme discussed in this report is designed to allow waste samples
to be safely collected and rapidly characterized for safe compositing and
further laboratory analysis. In addition, it will provide laboratory
personnel with valuable information and a head-start on the analysis of
the waste. It is devised to merge with a laboratory analysis scheme such
as the one being developed by the Region VII EPA laboratory. Together the
procedures will help fill in the gaps existing in the EPA priority pol-
lutant analysis procedures which were not designed with the intent to
completely analyze a hazardous waste as is desired for safe cleanup of
waste sites and is required by the Resource Conservation and Recovery Act
(RCRA).
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SECTION 2: SAFETY
There are numerous safety considerations which must be addressed when
preparing to obtain a sample and conducting an analysis procedure. The
tests outlined in this procedure have been designed to allow for the
separation of incompatable wastes and provide information necessary for
safe laboratory analysis as well as waste staging and removal operations.
The greatest danger to field personnel exists from the time an attempt is
made to open a closed container or obtain a sample until the waste has
been characterized to sufficiently assess the particular hazards of the
waste. Drum opening procedures and necessary safety measures are currently
being developed. All tests in the field portion of the analysis are to
be conducted a safe distance upwind from the site and only with a small
sample of the waste. All contaminated sampling and characterization materials
and protective gear must be decontaminated or disposed of properly.
Some additional safety considerations unique to specific tests will be
addressed later in the discussion of the procedure.
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SECTION 3: DOCUMENTATION
It is very important to develop a documentation procedure to be
initiated at the beginning of the waste characterization and continued
throughout the analysis procedure. There are many methods of documentation
which can be used as long as it identifies each waste or container and
allows each sample to be traced throughout its analysis.
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SECTION 4: PROCEDURE
The characterization and analysis procedure is divided into several
sections, beginning with a site characterization section for safety.
Each section consists of several steps or tests. The analysis precedes
consecutively through the steps unless as a result of a test the procedure
directs the analysis to another section or step, or the sample is included
into one of the waste categories listed below.
Typical Waste Categories
Group I: Air Reactive Group VII: Cyanide & Sulfide Wastes
Group II: Solids Group VIII: Inorganic Bases & Neutrals
Group III: Water Reactive Group IX: Organic Oxidizer
Group IV: Inorganic Oxidizer Group X: Organic Acids
Group V: Nitric Acids Group XI: Organic Bases & Neutrals
Group VI: Inorganic Acids
The above categories are not all inclusive, therefore, at some major
sites similar to Chemical Control, Elizabeth, N.J., or Seymour Recycling
Center, Seymour, .Ind., additional groups may be added such as radioactive
wastes, gas cylinders, resins and prepolymers, etc. On the other hand, at
smaller sites often only a few of the categories will be represented and
sometimes only one waste will be present. It is not possible to design
a characterization procedure which is suited to every site. Sometimes
portions of the procedure may be omitted or additional tests may need to be
added. Care must be taken when deleting steps not to omit a step which is
necessary to determine the safety of a step which it precedes. Each site *
needs to be considered individually.
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A narrative of the general categories and the analysis steps which
they include begins below. A condensed outline of the procedure which
numerically lists'the analysis steps begins on page 14.
A. Site Entry and Safety Characterization
Site entry procedures will vary on a case by case basis depending on
the nature of the site and how much is known about the site initially. If
there is ever any question over what safety measures or personal protection
is necessary, the higher level of protection should always be used until
sufficient information is obtained to deem the precautions unnecessary.
Several indispensable monitoring and survey instruments are an
explosive atmosphere meter, oxygen meter, draeger pump with hydrogen cyanide
tubes, radiation survey meter, and an organic vapor analyzer (OVA) or HNU
photoionization detector. There may be additional survey equipment necessary
at particular sites other than those listed above, such as a metal detector
or additional gas detector tubes. The radiation survey meter should be
equipped with a probe which is sensitive to alpha particles in addition to
beta and gamma radiation. At many sites each container will have to be
scanned for radioactivity after it is opened. All radioactive wastes
should be segregated for safety purposes and properly labelled to meet
shipping requirements. The HNU photoionization detector is not sensitive
to several flammable organic vapors such as methane, ethane and propane,
therefore, its use as a safety monitoring instrument is limited. A Century
organic vapor analyzer may be used for explosive atmosphere monitoring
unless the vapor concentrations are higher than the instruments full scale,
at which time a less sensitive explosion meter must be employed.
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B. General Visual Checks and Physical Characteristics
The steps in this characterization phase are very broad and will differ
greatly from site to site. All pertinent meteorological information and
geological characteristics should be recorded. A complete inventory
of the site may be conducted including the types and quantity of containers
present. Any customized containers or suspicious looking drums should
be noted for special handling and segregation. Record any evidence which
indicates the toxicity of the waste or potential hazards such as dead
plants or animals or bulging drums.
C. Sample Acquisition
Great care is required when opening drums or any sealed container.
A detailed drum opening procedure is not within the scope of this paper,
however, several methods are currently under development.
The air reactive wastes will be discovered during the opening or
sampling procedure. The air reactive substances normally require special
packaging. The wastes may be stored under water or some other liquid to
prohibit air from coming in contact with the waste. They may also be found
in sealed ampules, corregated drums, stainless steel cannisters, or
specially lined drums. Some chemicals such as white phosphorus or barium
azide react with the oxygen in the air while others react with the moisture
in the air such as cesium or various metal hydrides. Many of the air reactive
chemicals are explosive.
There may be drums containing various amounts of laboratory chemicals
(lab-packs). Lab-packs always have removable lids and often contain chemicals
which are incompatable. Any specialized or suspicious looking containers
require special handling and should be suspected of containing reactive
or explosive wastes. Gas cylinders may be encountered and should be
considered on a case by case basis depending on the condition of the cylinders
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and what they are suspected to contain.
Once the waste is found to be compatible with the ambient atmosphere,
the next step is- to collect a sample. Separate samples should be collected
for field characterization"and laboratory analysis.
Much of the initial characterization is performed in conjunction with the
sampling operation. The first step is to determine whether the waste is
a liquid, solid, semi-solid, or a mixture of solid and liquid. This
determination may be difficult and will require some experience and intuition.
Whether the waste will be redisposed of as a solid or liquid will play part
in this determination. A determination of the viscosity would be helpful
at this point. If the waste is a heterogeneous mixture, the solid and
liquid phases should be analyzed separately. Any observable characteristics
of the waste should be noted at this time. From this point, the liquids
and solids are characterized separately.
D. General Liquid Characterization
Liquids are usually sampled with a "thieving rod" or a similar pipette
type instrument. The sample may be examined through the glass rod for
invisible phases or other visual differences. If more than one phase is
present they should be separated for individual analysis. Generally, if
more than one phase is present one of them will be aqueous.
After collection, take the sample off-site or to a remote area of the
site for further characterization.
The first liquid characterization step is to perform a crude flammability
test with the waste. One or two drops of the waste are placed in a porcelain
spoon and held above the flame of a bunsen burner fueled by a portable
propane tank. The willingness of the waste to ignite should be recorded
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as well as any other observations such as flame color or sootyness. An
indication of the composition of the waste may be obtained from these
observations.. For instance, aromatic compounds generally produce a red sooty
flame. Also a Bielstiens halogen test is conducted at this time. A
small coil is made in the end of a copper wire and held in the flame until
any green color disappears. The wire is then dipped in the waste and
subsequently placed in the flame again. A green flame indicates the
presence of halogenated compounds. This test is surprisingly sensitive
and can often detect halogenated compounds at concentrations of less than
1.0%.
Next, several drops of the waste are placed in a small flask with water.
A water reactive waste is indicated by heat generation, gas generation,
or combustion. Many substances will develop some heat of solution or
change color in water but this does not necessarily designate a water
reactive waste. A liquid which is insoluble in water may be assumed to be
organic and advanced to section F of the characterization. Some organic
solvents such as acetone or alcohols are misible with water, but a mixing
reaction is usually readily detectable. Close observation is necessary
to prevent mischaracterization of these solvents. An aqueous waste will
form a single 'phase in the flask and be categorized as an inorganic liquid.
It is also important not to confuse emulsions for water soluble wastes.
E. Inorganic Liquid Characterization
It is advisable to run an Organic Vapor Analyzer (OVA) headspace
vapor scan of the waste to verify that the waste is aqueous and to determine
if any volatile organics are at detectable levels in the waste. If any
vapors are detected, further analysis with the gas chromatograph (GC)
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mode of the OVA may be desirable.
Strong inorganic oxidizers are detected next with potassium iodide/
starch paper. A color change to blue indicates the presence of an
oxidizer. If an inorganic oxidizer is detected, it should be analyzed
further to determine if it is nitric acid which is in a waste group of its
own. Also, a peroxide indicator paper may be used to detect inorganic
peroxides.
The pH of the waste is determined next, preferably with pH paper rather
than a meter as some wastes may harm a pH probe and it would be necessary
to clean the probe after each reading.
For the purpose of this characterization procedure, a pH of less than
three is considered acidic and a pH greater than or equal to three is considered
neutral or basic.
The "acidic wastes are tested for nitric acid by adding .5 ml of di-
phenylamine indicator (1 gram diphenylamine in 50 ml methanol) to a dilution
(2\
of the waste and subsequently adding dilute HoSOA' A color change to blue
indicates nitric acid. If the test is negative the waste is placed in
the inorganic acid group. The separation of nitric acid is necessary
because it is a strong oxidizer and is incompatible with many other wastes.
The basic and neutral wastes are tested for the presence of sulfide by
placing several drops on a strip of lead acetate paper. The paper will turn
dark if sulfide is present in the waste. Sulfide will interfere with the
following cyanide tests so it may be desirable to remove the sulfide in order
to determine if cyanide is also present in the waste, or it may be satis-
factory to composite the sulfide and cyanide wastes for further analysis
or disposal. If the first option is chosen, the sulfide can be removed by
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adding cadmium nitrate to the sample in order to precipitate out cadmium
sulfide. Periodically, repeat the lead acetate test to determine when the
sulfide is completely removed.
Cyanide may be found with a cyanide detector tube available from HACH
Chemical Company or a silver nitrate/rhodanine test may be used. The detector
tube method consists of partially submerging a tube which has had its tips
removed in a dilution of the waste. A discoloration in the tube represents
the presence of cyanide. The second method involves adding several drops of
rhodanine indicator (20 mg p-dimethyl-amino-benzalrhodanine in 100 ml
acetone) to a dilution of the sample, then adding an excess of silver
(3}
nitrate sblutionv '. A color change from yellow to brownish-pink indicates
cyanide. The detector tube method is more expensive and probably uses the
same reagent and indicator but it is easier to use.
If the sulfide and cyanide tests are both negative, the waste is
placed in a group for inorganic bases and neutrals. The wastes in each
group may now be composited for further laboratory analysis. Care should
be taken when compositing the wastes and close observation is necessary to
detect any reactions between the wastes. It is advisable to monitor
the sulfide and cyanide wastes with a Draeger pump and tubes while com-
positing to detect the evolution of hydrogen sulfide or hydrogen cyanide.
Laboratory analysis of the water soluble liquids will include a total
organic carbon (TOC) test to determine the presence of small amounts of
organic compounds. The TOC procedure may denote that additional organic
analysis is necessary.
Similarly, a total dissolved solids test will indicate if cation and anion
analysis is necessary. Additional laboratory tests such as E. P. toxicity or
corrosivity specified in the Resource Conservation and Recovery Act (RCRA)
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may also be conducted.
F. Organic Liquid Characterization
The majority of the organic wastes which are disposed of nationwide
consist of spent solvents, sludges from solvent reclamation, or other wastes
which contain organic solvents as a significant portion of their volume.
These solvents are usually volatile enough to be readily detected in the
headspace above the waste with an OVA or HNU photoionization detector. The
number of different commonly used solvents is not great, therefore, an
experienced analyst equipped with a GC modified OVA or other portable
flame ionization detector GC and standards of the common solvents can often
identify the solvent present in the waste. Several of the common solvents
such as mineral oils or stoddard solvents consist of mixtures of different
chemicals, but these can also often be identified by a characteristic
"fingerprint" produced by the separate components on a chromatogram. If
there are no detectable vapors above the waste, it can be assumed to
consist of non-volatile organics. For instance, PCB oils may not have any
volatile components.
Organic oxidizers and peroxides are detected with potassium iodide/
starch paper and peroxide indicator paper as in the inorganic liquid
character!' zati on.
Organic acids are found by adding the waste and distilled water to a
small flask or vial at a 2:1 ratio, swirling, and determining the pH of
the water. Organic acids are usually only slightly soluble in water, therefore
accuracy in the pH readings are important.
The viscosity of the waste should be determined in the field or laboratory.
The importance of this step will vary depending on the site and what wastes
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are present at the site. It is important in determining the method
by which the waste may be transported or removed from the site. It
can be used to. determine if a waste may be pumped into a tank and unloaded
from a tank truck. It may be desirable to form a separate group for the
highly viscous resins and prepolymers.
Samples of the wastes in the individual organic groups may be com-
posited for laboratory analysis. Laboratory analysis of the organic liquids
will include an infra-red scan to determine the molecular structural
features of the major constituents of the waste followed by further GC/MS
analysis.
G. Solids Chracterization
The solids may consist of a large variety of wastes. Many of the
reactive and explosive wastes fall into this category. Keep in mind the
considerations on reactive and explosive wastes discussed earlier in
the report.
Often, a great deal can be determined about the hazards of a waste
by the way it is packaged and its physical characteristics such as texture,
color, density, etc. If a waste is packaged to exclude water, i.e.,
plastic lined or water tight containers, it should be treated as a water
reactive waste until proven otherwise. Conversely if a waste is moist or
contains water, it should not be allowed to dry out until sufficient tests
have been conducted to show that it is not explosive when dry.
Many of the tests for solids are similar or identical to those for
liquid wastes. The Bunsen Burner flammability test discussed earlier should
be carefully conducted as well as the Bielstierfc copper wire halogen test
if it is feasible. Also, a test for ignitability by friction or a strong
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initiating force would be helpful.
There are several tests to be conducted after placing a small amount
of the waste in a small flask with distilled water and the waste is determined
not to be water reactive. A rough determination of the solubility of the
waste in water is made before determining the pH of the solution. Many
solid wastes are alkaline. Generally, a waste which significantly dissolves
in water is inorganic.The oxidizer, peroxide, sulfide, and cyanide spot
tests should be conducted on the waste/water mixture. Solids with similar
properties may be composited for laboratory analysis.
The laboratory will begin analysis by dividing the solids into
water soluble and water insoluble categories and determining the percent
moisture and percent volatile solids in the wastes. Further RCRA,
organic and inorganic analysis will follow as deemed necessary.
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SECTION 5: CONDENSED PROCEDURE FOR FIELD CHARACTERIZATION OF HAZARDOUS WASTE
A. Site Entry and Safety Characterization (After background sources and
off-site recon resources have been exhausted).
Level "A" protection
1. Determine the percent of the lower explosive limit (L£L) of
vapors in the atmosphere with an explosion meter while continually
monitoring the oxygen level.
2. Test for hydrogen cyanide with a Draeger pump and tubes.
3. Test for radioactivity.
4. Continually monitor with an organic vapor analyzer (OVA) or
photoionization detector (HNU).
B. General Visual Checks and Physical Characteristics.
; 5. Record air temperature and other pertinent meteorological in-
formation and geological characteristics.
6. State of containers (corrosion, bulging drums, etc.).
7. Other non-specific information (dead plants or animals, plant
stress, labels on drums, etc.).
C. Open Container and Obtain a Sample (Drum opening techniques and safety
measures are not within the scope of this procedure).
8. Group I: Air Reactive - Determine if the waste is air reactive.
If yes - Stop characterization at this point.
If no - Proceed to Step 9.
9. Determine if it is a liquid, solid, semi-solid, or heterogeneous
mixture, and estimate its viscosity.
Liquid - Go to D
Solid - Go to G (Group II - Solids)
Semi-Solid - Go to D and G
Heterogeneous - Possibly separate phases and go to D and G.
D. General Liquid Characterization
10. Perform an open flame ignitability test and Bielstien's copper wire
halogen test and record results.
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11. Check for mil Hi phases. If there is more than one phase it may be
possible to separate the phases and analyze them individually.
12. Determine if it is soluble, insoluble, or reactive with water
by placing several drops in a small flask with water. This
should be done a safe distance from the site.
Group III: Water Reactive—Check for any reaction with water:
heat generation, gas generation, combustion, etc.
There is often some heat of solution or color change
when the waste is mixed with water but this should
no£ be considered a water reactive substance.
Organic Liquid Waste - An organic (non-aqueous) liquid will
not readily mix with water. Some exceptions to
this are solvents such as acetone and alcohols,
however, the mixing reaction of these solvents is
usually easily detectable. Go to F.
Aqueous (Inorganic) Waste - An aqueous waste will form a single
phase in the flask. Go to E.
E. Inorganic Liquid Characterization
13. Check for the presence of soluble volatile organics with OVA or HNU.
If present - Further organic analysis in lab or with GC mode
of OVA may be desirable.
If absent - Go to 14.
14. Check for an inorganic oxidizer with Kl/starch paper and peroxides
with peroxide indicator paper.
If positive - Group IV: Inorganic Oxidizer.
If negative - Go to 15.
15. Determine pH of waste.
If acidic (pH<3) - Go to 15.
If neutral or basic (pHi3) - Go to 16.
16. Detect the presence of nitric acid with a ^SO^/diphenylamine
indicator.
If positive - Group V : Nitric Acid
If negative - Group VI: Inorganic Acid
17. Check for the presence of sulfide with a lead acetate paper test
and test for cyanide with a HACK cyanide detector tube or a
silver nitrate/rhodanine test.
If either test is positive - Group VII: Cyanide or Sulfide Waste
If both tests are negative - Group VIII: Inorganic Bases and Neutrals
18. Laboratory analysis of inorganic wastes. With the exception of
Groups I and II, wastes which are in the same group may be com-
posited for lab analysis.
a. Total dissolved solids and total organic carbon (TOC).
b. Cation and anion analysis.
c. Organic analysis if necessary.
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F. Organic Liquid Characterization.
19. Check for the presence of volatile organics with an OVA or HNU.
If.present - Further volatile organics analysis with the GC
mode of the OVA may be desirable.
If absent - The waste consists of heavier non-volatile
organics. Go to 20.
20. Check for an organic oxidizer with KI/starch paper and peroxides
with peroxide indication paper.
If positive - Group IX: Organic Oxidizers and peroxides
If negative - Go to 21.
21. Check the pH of a distilled water shakedown of the organic.
If acidic - Group X: Organic Acids.
If neutral or basic - Group XI: Organic Bases and Neutrals.
22. Determine the viscosity of all the organic wastes mechanically or
visually.
23. Laboratory analysis of the organic wastes. The wastes of the
separate organic groups may be composited with the exception of
some viscous wastes.
a. Infra-red analysis for determining molecular structural
features.
b. Volatiles, Base/Neutrals, Acids, Pesticides by GC/MS and GC.
G. Solids Characterization - Group II: Solids
24. Record color, texture, density, etc.
25. Perform open flame ignitability test and Bielstien's copper wire
halogen test if possible.
26. Place a small amount in a small flask or vial with water. This
procedure should be conducted a safe distance from site.
a. Check for reactivity with water and estimate the
solubility of the waste in water. This is a rough estimate.
b. Determine the pH of the Mixture.
c. Check for an oxidizer with KI/starch paper and peroxides
with peroxide indication paper.
d. The cyanide and sulfide spot test in test #17 may be
conducted.
27. Solids Laboratory analysis. Solids with similar properties above
may be composited.
a. Percent moisture and percent volatile solids.
b. Inorganic and organic analysis as deemed necessary.
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SECTION 6: CONCLUSION
The characterization protocol discussed in this report is designed
as a cost effective means to enable field personnel to characterize and
begin to analyze hazardous waste in the field. It allows incompatable wastes
to be separated and compatable wastes to be composited for further analysis
or staged for proper disposal. A laboratory procedure devised to analyze
hazardous waste can begin where this procedure terminates in order to
further identify and quantify the components->of the waste.
A prototype field kit, which will enable the methods discussed in this
report to be efficiently conducted in the field, is being developed. An
inventory of the supplies in the kit as well as field instructions and
data sheets will be included in a final report on the characterization
procedure.
A flow sheet summarizing the field characterization procedure is shown
in Figure 1. .
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Contents Unknown
Group II: Solids
Solids Lab
Analysis
00
Group IX: Organic Oxidizei
Group X: Organic Acids
Group I: Air Reactive
liquid
Group III: Water
Reactive
Group XI: Organic
Bases and Neutrals
Group VI:
Inorganic Acids
Water Insoluble
Lab Analysis
.inorganic
liquid
Group IV: Inorganic Oxidizer
Group V:
Nitric Acid
Group VIII: Inorgani
Bases and Neutrals
Group VII: Cyanide
and Sulfide Wastes
Water Soluble
Lab Analysis
Figure 1: Flow diagram of the procedure for Field Characterization of
Hazardous Waste. The numbers represent the corresponding
tests in the procedure.
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REFERENCES
1) Shriner, et. al., The Systematic Identification of Organic Compounds,
5th ed., John Wiley and Sons, New York, N.Y., 1964.
2) Windholz, et. al., The Merck Index, 9th ed., Merck & Co., Inc.;
Rahway, N.J., 1976.
3) Franson, et. al., Standard Methods for the Examination of Hater and
Wastewater, 14th ed., American Public Health Association; Washington,
D.C., 1975.
ACKNOWLEDGEMENTS
I would like to thank Fred Klotzbach of Ecology and Environment,
Inc. and Dr. John Connolly of the UMKC Chemistry staff for their
valuable contributions and suggestions.
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