v>EPA
TVA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-81-094
May 1981
Tennessee Valley
Authority
Office of Power
Energy Demonstrations
and Technology
Chattanooga TN 37401
TVA/OP/EDT-81/25
Halogenated Organics
Study for Allen,
Kingston, and Shawnee
Steam Plants
Interagency
Energy/Environment
R&D Program Report
L
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
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The nine series are:
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4. Environmental Monitoring
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This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
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Development Program. These studies relate to EPA's mission to protect the public
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tems. The goal of the Program is to assure the rapid development of domestic
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tion Service, Springfield, Virginia 22161.
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EPA-600/7-81-094
May 1981
Halogenated Organics Study
for Allen, Kingston, and
Shawnee Steam Plants
by
C.V. Seaman, H.B. Flora II, and LO. Hill (TVA);
B.W. Vigon, T.B. Stanford, and M.D. Hunter (Battelle-Columbus)
TVA, Division of Energy Demonstrations and Technology
1140 Chestnut Street, Tower II
Chattanooga, Tennessee 37401
Interagency Agreement No. D5-E721
Program Element No. 1NE624A
EPA Project Officer: Julian W. Jones
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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DISCLAIMER
This report was prepared by the Tennessee Valley Authority and has
been reviewed by the United States Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Tennessee Valley
Authority or the United States Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
11
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ABSTRACT
This report summarizes the results obtained from studies to determine
halogenated organic formation in chlorinated cooling waters at TVA's Allen,
Kingston, and Shawnee Steam Plants from June through December 1979. Conden-
ser cooling water samples were collected and transported to TVA's Laboratory
Branch for analysis. These samples were collected at various sites through-
out the condenser cooling water system from the plant intake through the
condenser outlet.
Based on the data gathered, it appears that low levels (generally
<20 ppb) of some halogenated organic compounds, mainly volatile ones,
are formed during power plant chlorination. Only chloroform was detected
more than 90 percent of the time at any location. Three semivolatile
halogenated organic compounds were detected. Chlorine dosage appears to
be directly related to the level of the halogenated organics identified
in the condenser cooling water system.
It was determined that precursors show consistent measurements above
the detection limit of the analysis techniques. Bromide, ammonia, color,
and fulvic acid concentrations were higher at the Allen Plant than the
other two plants. The average humic acid concentration was similar at
all plants. A temporal trend was also apparent in the data. However,
there is no clearcut pattern that supports any relationship between pre-
cursors such as humic acid, fulvic acid, or amino acids and halogenated
organic compounds.
Results of the amino acid data showed consistent measurement below
the detection limit of the analysis techniques. The data displayed no
apparent temporal trends and no tendency toward one class or structural
type of amino acid.
111
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TABLE OF CONTENTS
Abstract iii
Figures v
Tables vi
Acknowledgement vii
Chapter
I. Introduction 1
II. Conclusions and Recommendations 4
III. Objectives 6
IV. Approach 7
V. Chemistry 11
VI. Description of Plants 14
VII. Description of Analytical Procedures, Sample
Preparation, and Sample Handling Procedures 17
VIII. Statistical Analysis 27
References 67
Appendixes
A. Data for Volatile and Semivolatile Halogenated
Organics for all Plants A-l
B. Data for Precursors, Amino Acids, and Water Quality
for all Plants B-l
C. Quality Assurance Data C-l
IV
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FIGURES
Figure Page
1. Chloroform - Concentration Versus Location 41
2. Chloroform - Concentration Versus Location for all
Data 42
3. Chloroform - Concentration Versus Month/Day for
Inlet 12 Minutes 43
4. Chloroform - Concentration Versus Month/Day for
Outlet 12 Minutes 44
5. Scattergram of Chloroform Versus Chlorine Dosage 60
6. Scattergram of Chloroform Versus Free Chlorine
Residual 61
7. Scattergram of Chloroform Versus Nitrogen Species 62
8. Scattergram of Log Chloroform Versus Log Substrate .... 63
9. Scattergram of Log Chloroform Versus Log Nitrogen
Species 64
v
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TABLES
Table Page
1. Halogenated Organics Determined During the Study 2
2. Precursors Monitored During the Study 9
3. Amino Acids Monitored During the Study 10
4. Raw Water Quality at the Allen Steam Plant 14
5. Raw Water Quality at the Shawnee Steam Plant 15
6. Raw Water Quality at the Kingston Steam Plant 15
7. Purge-and-Trap and GC Parameters for Volatile
Halogenated Organics 22
8. GC-MS Parameters for Acidic Semivolatile
Halogenated Organics 23
9. GC-ECD Parameters for Neutral Semivolatile
Halogenated Organics 24
10. Halogenated Organic Compound Detection Frequency
Summary - Allen Plant 29
11. Halogenated Organic Compound Descriptive Statistics -
Allen Plant 30
12. Precursors - Descriptive Statistics - Allen Plant 32
13. Halogenated Organic Compound Detection Frequency
Summary - Kingston Plant 33
14. Halogenated Organic Compound Descriptive
Statistics - Kingston Plant 34
15. Precursors - Descriptive Statistics - Kingston Plant. ... 36
16. Halogenated Organic Compound Detection Frequency
Summary - Shawnee Plant 37
17. Halogenated Organic Compound Descriptive
Statistics - Shawnee Plant 38
18. Precursors - Descriptive Statistics - Shawnee Plant .... 39
19. Simple Correlations, Allen, Intake 51
20. Simple Correlations, Allen, Inlet 52
21. Simple Correlations, Allen, Outlet, Time 1 53
22. Simple Correlations, Allen, Outlet, Time 2 54
23. Simple Correlations, Allen, Outlet, Time 3 55
24. Simple Correlations, Allen, Outlet, Times 1 and 2
Combined 57
25. Partial Correlations Matrix - Allen, Outlet, Times
1 and 2 58
VI
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ACKNOWLEDGEMENTS
We would like to express our appreciation to the following TVA
organizations for their support during this study:
Division of Fossil and Hydro Power
Fossil Operations - W. H. Thompson
B. E. McCuiston, Allen Steam Plant, Superintendent
L. B. Kennedy, Kingston Steam Plant, Superintendent
T. D. Womble, Shawnee Steam Plant, Superintendent
Division of Natural Resource Services
Laboratory Branch - C. W. Holley, D. G. Carpenter,
L. 0. Hill, B. S. Neal, W. R. Scott, T. S. Hobbs
A special appreciation is extended to B. W. Vigon, T. B. Stanford,
and M. D. Hunter of Battelle-Columbus Laboratories, Columbus, Ohio; and
to the Results Sections of each steam plant for their continued coopera-
tion and support throughout this study.
VII
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CHAPTER 1.
INTRODUCTION
Because of interest in organic contaminants and the concern as to
their significance, the Environmental Protection Agency (EPA) conducted
tests in cities across the country to measure the concentrations of six
halogenated compounds in raw and finished waters.1 The resulting data
led to the establishment of halogenated organics on the priority pollutant
list.
It has been assumed that halogenated compounds are formed as a direct
result of the chlorination process used by the water treatment facilities.
It is also assumed that these compounds are formed by the chlorination
process used to reduce biofouling in the cooling water systems of fossil
fueled and nuclear power plants.
Although not final, EPA has proposed water quality criteria for many
halogenated compounds.2 There are questions regarding the significant
production of halogenated compounds in chlorinated cooling water systems.
This report presents data regarding the formation of halogenated compounds
in chlorinated cooling water systems. Table 1 lists the volatile and
semivolatile halogenated compounds of concern during this study.
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TABLE 1. HALOGENATED ORGANICS DETERMINED
DURING THE STUDY
Volatiles:
Chloroethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
Bis-(chloromethyl)-ether1
1,1-dichloroethylene
Trans-1,2-Dichloroethylene
1,2-Dichloropropane
1,3-Dichloropropane
Bromoform
Chloroform
Methyl Chloride
Methyl Bromide
Methylene Chloride
Carbon Tetrachloride
Chlorobenzene
Bromodichloromethane
Trichlorofluoromethane
Dichlorodifluoromethane
Dibromochloromethane
Semivolatiles:
Base-Neutral Compounds
Hexachloroethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2,4-Trichlorobenzene
Tetrachlorobenzene
Pentachlorobenzene
Hexachlorobenzene
Bis-(2-chloroethyl)-ether
Tetrachloroethylene
2-Chloronaphthalene
2-Chloroethyl vinyl ether
1. This compound has been removed from the list since it is very
unstable in water (tj = 52 s) and would not be expected in any of
these water samples.
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Table 1. (Continued)
Acidic Phenols Compounds
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
Dichlorophenol
Trichlorophenol
Tetrachlorophenol
Penta chlo ropheno1
Monochlorocresols
Dichlorocresols
Trichlorocresols
Tetrachlorocresols
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CHAPTER II.
CONCLUSIONS AND RECOMMENDATIONS
Data on volatile and semivolatile halogenated organic compounds were
obtained at three TVA power plants over a four- to six-month period in
1979. Samples were analyzed at three locations—plant intake, condenser
inlet, and condenser outlet—and several times prior to, during, and fol-
lowing a chlorination cycle. On selected dates samples were also ana-
lyzed for a variety of precusors thought to influence the halogenated
compound concentrations.
Volatile halogenated organic compounds were detected with variable
frequency as a function of plant and sample location. Only seven volatile
halogenated organic compounds and three semivolatile halogenated organic
compounds were detected. By far chloroform, being detected at each plant
in excess of 90 percent of the time, was the most frequently encountered.
Other volatile halogenated organics frequently detected were bromodichloro-
methane and dibromochloromethane. Other volatile halogenated organics
occasionally found were: 1,2-dichloroethane; trans-1,2-dichloroethylene;
methylene chloride; and 1,1,1-trichloroethane. The semivolatile haloge-
nated organic compounds detected were: 2-chloronapthalene; 2-chlorophenol;
and 1,2-dichlorobenzene. All compounds except chloroform had an average
detection frequency of less than 70 percent at all plants. The highest
concentration of chloroform analyzed was 18.0 |Jg/l as compared to the
24-hour criteria level for fresh water (500 |Jg/l).
The large number of precursor categories (27 in all) necessitated
some selection procedure to limit the number of categories tested for a
relationship with the halogenated organic compounds. By concentrating
on the current mechanistic arguments for the halogenation reaction(s)
and by constructing composite variables from several precursor categories,
the following subset was obtained:
Chlorine dosage
Free residual chlorine (inlet)
Total residual chlorine (inlet)
Temperature
- pH
Bromide
• Nitrogen species
Substrate
The value of the nitrogen species variable was calculated by adding
the concentrations of ammonia-nitrogen, organic nitrogen, and amino acids.
The value of substrate was obtained by summing the concentrations of humic
and fulvic acids.
Most of the correlation analysis effort centered on the data obtained
at the Allen Plant since this was the most extensive set. Although indivi-
dual sample locations provided some insight, it was the analysis of the
inlet and two outlet samples during a chlorination cycle which proved
most productive.
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At the inlet and outlet, time 1 and 2, some interesting relationships
appear. In particular the outlet chloroform versus chlorine dosage rela-
tionship becomes important and so does the correlation between chloroform
and nitrogen species. Both the positive relationship with chlorine dose
and the negative relationship with nitrogen species are consistent with
the currently accepted trihalomethane formation mechanism. And when con-
trolling chlorine dosage and bromide ion effects, the original correlation
is strengthened.
The pH level was significantly and negatively correlated with chloro-
form only when the effects of nitrogen species concentrations and chlorine
dosage were removed.
A similar trend was found for bromide ion, but the results were more
difficult to interpret. Control of chlorine dosage and substrate produced
a positive relationship while other correlations were negative. Since a
negative correlation coefficient implies an antagonistic relationship
between chloroform and bromide, this result is consistent with a mechanism
involving bromide oxidation by chlorine.
Substrate was correlated significantly with chloroform concentration
only when the effects of chlorine dosage were removed. This was inter-
preted to mean that the substrate-chloroform interaction was indeed pre-
sent, but strongly influenced by the substrate-dose relationship.
The effects of temperature were difficult to analyze. None of the
correlations indicated a linear relationship with the data from Allen.
However, combining the data across plants for the outlet location and
removing the effects of other precursors produced a significant relation-
ship. This suggests that temperature influences on chloroform concentra-
tion are masked by effects of other variables on chloroform concentrations.
It is concluded that most aspects of the current hypothesis concerning
the factors affecting chloroform production during chlorination can be
supported by actual field test data. Several of the relationships are
masked by the effects of other variables on chloroform.
Future research should focus on a detailed study at a single plant
to provide a sufficient data base to analyze without combining several
sample locations. Studies should attempt to collect data while control-
ling the parameters of chlorine dosage and condenser cooling water flow
rate.
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CHAPTER III.
OBJECTIVES
This study was conducted to provide a reconnaissance of the magni-
tude of volatile and seraivolatile halogenated organics produced in a
once-through cooling water system. The objectives of this project were:
(1) to determine the concentration of specific halogenated organics that
exist in the plants cooling water source; (2) to identify compounds pro-
duced in the chlorination process and discharged by the plant; (3) to
determine the relationship of newly formed compounds to water quality;
and (4) to determine any correlation between suspected precursors with
the halogenated products.
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CHAPTER IV.
APPROACH
This study included three TVA fossil fuel steam plants (Allen Steam
Plant, Kingston Steam Plant, and Shawnee Steam Plant) with once through
cooling systems. These plants were chosen-for this TVA test primarily
because of the chlorine minimization studies that were conducted during
1979 at each site. Samples were collected at the following points at
each plant: (1) plant intake, (2) condenser inlet, and (3) condenser
outlet.
All samples were collected and analyzed for volatile and semivolatile
halogenated organic compounds. The intake samples documented the com-
pounds which were present when the cooling water entered the plant and
concentrations of those compounds. Samples were collected at the inlet
and outlet of the condenser to determine specific halogenated organic
compounds and the concentrations produced by the plant chlorination
process.
The chlorination process may be a factor contributing to the forma-
tion of halogenated organics. It is during this process that precusors
present in the river source are possibly combined with chlorine to form
halogenated organics. Samples were, therefore, taken during the process
to determine: (1) whether the formation is instantaneous or whether there
is a time interval before the formation begins; and (2) what compounds
are formed and their concentrations.
Initially, samples were collected during the chlorination cycle-one
sample from the inlet and several from the outlet. Analyses of these
samples should help determine whether the formation of compounds is greater
during any one time of the chlorination cycle. Samples were also collected
after the chlorination cycle was finished to determine at what point in
time the formation of halogenated organics had stopped.
Raw river water samples were collected and analyzed for precursors
(Table 2) and amino acids (Table 3). The goal was to determine the pres-
ence of each class of compound and provide a semiquantitative measure of
the levels of each.
Presampling preparation and sampling procedures were based on techni-
ques set forth by the U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio,3 and the Division
of Natural Resources Services, Laboratory Branch. These procedures repre-
sent current state of the art, but improvements and modifications were
anticipated as more experience was obtained during the study.
All samples were collected and immediately cooled to 0°-4°C by packing
them in ice. The samples for volatile and semivolatile organic compounds
were immediately transported to the Laboratory Branch for analysis. The
samples for bromide, polyhydroxybenzenes, humic acid, fulvic acid, natural
color, and amino acids were shipped to an independent research laboratory
which has the capabilities to perform these analyses. The procedures
used for all analyses are described in Chapter VII.
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The data gathered through this effort should provide information
regarding the formation of halogenated organics in a chlorinated once-
through condenser cooling water system. It should also help TVA and the
power industry address questions regarding the production of these com-
pounds in power plant cooling water systems.
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TABLE 2. PRECURSORS MONITORED DURING THE STUDY
Free Chlorine (Inlet)
Free Chlorine (Outlet)^a)
Total Chlorine (Inlet)^
Total Chlorine (Outlet)^
fa)
Chlorine Dosage (Calculated)v '
fa)
Circulating Cooling Water Flow
(a)
Organic nitrogen
A • -4. (a,b)
Ammonia-nitrogen '
fa)
Nitrate/Nitrite*1 '
fa)
Total Organic Carbonv '
Alkalinity^3^
Iron(a)
Calcium
Magnesium
fa)
Hardness
fa)
Temperature (Inlet)v }
fa)
Temperature (Intake)
fa)
Temperature (Outlet) *• }
fa)
Total Suspended Solidsv J
fa)
Specific Conductance
Bromide
Polyhydroxybenzenes
Humic Acids
Fulvic Acids
Natural
(a)Analyzed by TVA Laboratory Branch
(b)Analyzed by Battelle-Columbus Division Laboratories
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TABLE 3. AMINO ACIDS MONITORIED DURING STUDY
1. Alanine
2. Arginine
3. Asparagine
4. Aspartic Acid
5. Cysteine
6. Glutamine
7. Glutamic Acid
8. Glycine
9. Histidine
10. Isoleucine
11. Leucine
12. Lysine
13. Methionine
14. Phenylalanine
15. Proline
16. Serine
17. Threonine
18. Tryptophan
19. Tyrosine
20. Valine
10
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CHAPTER V.
CHEMISTRY
Natural waters may contain a great number of different organic mate-
rials. The extensive review of Vallentyne4 described thousands of com-
pounds of widely diverse types that have been found in natural waters.
The major source of organic matter in unpolluted water supplies is
plant material. This plant material can be synthetic units, metabolic
intermediates, end products, or decomposition residues of the biochemical
activities of members of the plant kingdom ranging from bacteria and algae
to forest trees.5 From these sources there are many individual chemical
components that may be encountered. The broad classes of chemical compounds
that may be found are: carbohydrates, proteins, lipids, nucleic acids,
terpenoids, carotenoids, chlorophylls, vitamins, carboxylic acids, esters,
amino acids, phenolic compounds, steroids, and humic substances. The fol-
lowing discussion reviews the likely chlorination reactions for some
diverse classes of organic compounds listed.
The central and most significant fact about aqueous chlorination, in
the range of concentrations employed in water treatment, is that elemental
chlorine, C12, is not involved. When chlorine is dispersed in water, C12
is hydrolyzed instantaneously and completely in accord with the equation
C12 + H20 -»• HOC1 + H+ + Cl" (1)
then hypochlorous acid dissociates by the following equation
HOC1 -> H+ + OCl" (2)
So, the reactions of hypochlorite rather than those of C12 should be
considered in describing the potential interactions of dilute aqueous
chlorine with organic compounds. There are four principal types of reac-
tions of hypochlorite with organic matter in aqueous solutions. These are:
(1) Addition5'6
H H H H
it (I
Ri - C = C - R2 + HOC1 -»• R! - C - C - R2 (3)
II
OH Cl
(2) Substitution5'6
C6H5OH + HOC1 -> C6H4C10H + H20 (4)
0 0
CH3C - CH3 + HOC1 •* CH2C1 - C - CH3 + H20 (5)
11
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(3) Oxidation, with reduction of the hypochlorite chlorine to chloride5'6
R - CHO + HOC1 -> RCOOH + H+ + Cl" (6)
(4) Substitution of chlorine for hydrogen on a nitrogen atom5'6
RI - N - R2 + HOC1 -> RI - N - R2 + H20 (7)
H Cl
In reactions 1 and 2, formation of the chlorinated derivative is pre-
ceded by an ionization and formation of a nucleophile (C ) to which the
positive chlorine of the hypochlorite in (OC1) becomes attached.7'8
The first three types of reactions convert the chlorine either to
chloride ion or to a covalently bound state in which the chlorine no longer
acts as an oxidizing agent toward readily oxidized materials. These reac-
tions may be considered part of the chlorine demand, which may be described
as the conversion of active chlorine to a non-oxidizing form.
The most important organic materials in natural waters are the humic
and fulvic acids, which account for about 90 percent of the dissolved
organic carbon in most waters. These compounds have been hypothesized as
being responsible for the formation of halogenated organics.
From these organic acids, trihalomethanes, such as chloroform (CHC13),
are produced.6 One reaction pathway for the formation of the trihalome-
thanes is the haloform reaction. This reaction generally occurs in alka-
line aqueous solutions with organic compounds containing the acetyl
0
II
group, CH3 - C -, or with structures such as CHgCHOH-that may be oxidized
to the acetyl group. The three hydrogens of the methyl group are replaced
by three halogen atoms and the carbon bond to the carbonyl group is split
giving rise to a haloform and a carboxylic acid. This reaction may be
written:
CH3COR + 3HOX •* CX3COR + 3H20 (8)
CX3COR + H20 -> CHX3 + RCOOH (9)
where x = Cl, Br, F, or I.
The mechanism for the halogenation reaction is an initial proton dis-
sociation from the alpha carbon which yields an enolate carbanion which is
then subject to electrophilic attack by HOC1 or OC1. Subsequent dissocia-
tion and addition of positive halogen continue until full halogenation is
achieved. A nucleophilic base attack displaces the CX3 group, which
combines with H to give the haloform.5 The mechanisms for these reactions
are:
0~
RCOCH3 •* RC = CH2 + H+ (10)
0"
RC = CH2 + HOX -> RCOCH2X + OH" (11)
12
-------
0
RCOCH2X -> RC = CHX + H+ (13)
0" 0
I II
RC = CHX + HOX -> RCCHX2 + OH (14)
0"
RCOCHX2 •* RC = CX2 + H+ (15)
0~
RC = CX2 + HOX •* RCOCX3 + OH" (16)
RCOX3 + OH" -» RCOOH + CX3" (17)
CX3~ + H+ •* CHX3 (18)
Ethanol, acetaldehyde, methyl ketones, and secondary alcohols with
the general formula CH3CHOHR are among the compounds or classes of com-
pounds that give the haloform reaction. Thus, sources of haloforms are
very extensive.
Chlorine chemistry has shown that chlorine is consumed through complex
sequential and parallel reaction pathways leading to both desirable and
undesirable reaction products.9'10 These undesirable products are the tri-
halomethanes (THM's). The formation of these trihalomethanes is not well
understood due to the complexity of the reactions between chlorine and
organic constituents in natural water.9'10 The rates of these reactions
are generally unknown.
In view of the lack of knowledge on the rates of the multiple reaction
pathways, kinetic models of THM formation have not yet been developed.9
Until such time the kinetic models can be developed, the quantitative under-
standing and control of the formation of THM's will be limited.
13
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CHAPTER VI.
POWER PLANT DESCRIPTIONS
Each of the three plants studied is located near different cooling
water sources. The Allen Plant is located on a tributary to the Missis-
sippi River near Memphis, TN; the Shawnee Plant is located on the Ohio
River just west of Paducah, KY; and the Kingston Plant is located at the
confluence of the Clinch and Emory Rivers west of Oak Ridge, TN. All
three plants utilize once-through condenser cooling systems. Only one
unit of each multi-unit plant was sampled.
Allen Steam Plant
This plant was sampled from June 5 to December 11, 1979. During this
period the following raw water characteristics were observed (Table 4).
TABLE 4. RAW WATER QUALITY AT THE ALLEN STEAM PLANT
Parameter
Maximum Minimum Median
Calculation for chlorine concentration is;
After 10 minutes.
Feed Rate lb/24 hrs
Flow Rate gal/min
Mean
pH, Std. Units
Total Suspended Solids, mg/1
Total Organic Carbon, mg/1
Ammonia (field), mg/1
Ammonia (lab), mg/1
Organic Nitrogen, mg/1
Chlorine Concentration, mg/1
Chlorine Demand, mg/1
7.7
29.0
6.6
0.32
0.20
0.40
1.53
0.63
7.1
10.0
5.0
0.02
0.01
0.21
0.80
0.31
7.3
11.0
5.2
0.05
0.02
0.27
1.13
0.46
_
15.0
5.7
0.12
0.08
0.42
1.13
0.47
83.22 = mg/1
During this monitoring period the unit load varied from 152 to 275
MW with an average of 207 MW, and the cooling water flow varied from about
86,670 gpm to 135,580 gpm averaging 116,910 gpm. Unlike the Kingston and
Shawnee plants, the Allen condenser is a two-pass condenser; that is, the
water completes two trips through the condenser before being discharged
to the receiving water body. The chlorination cycle lasts for 30 minutes
for each unit.
Shawnee Steam Plant
The Shawnee Plant was sampled from June 12 to November 6, 1979.
intake water quality was measured for the same parameters that were
monitored at Allen (Table 5).
The
14
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TABLE 5. RAW WATER QUALITY AT THE SHAWNEE STEAM PLANT
Parameter
Maximum Minimum Median
Calculation for chlorine concentration is:
After 10 minutes.
Feed Rate lb/24 hrs
Flow Rate gal/min
Mean
pH, Std. Units
Total Suspended Solids, mg/1
Total Organic Carbon, mg/1
Ammonia (field), mg/1
Ammonia (lab) , mg/1
Organic Nitrogen, mg/1
Chlorine Concentration, mg/1
Chlorine Demand, mg/1
7.4
39.0
5.8
0.03
0.02
0.18
0.75
0.24
7.3
28.0
3.0
0.01
<0.01
0.11
0.61
0.13
7.3
34.0
4.4
0.02
<0.02
0.15
0.68
0.18
_
34.0
4.4
0.02
<0.02
0.15
0.68
0.18
x 83.22 = mg/1.
During the monitoring period, plant load and cooling water flows were
noted. Plant unit load on the sampling dates ranged from 100 to 137 MW.
Cooling water flows spanned a range of 96,670 gpm to 121,930 gpm. The
chlorination cycle at the Shawnee Plant is 45 minutes per unit, which is
longer than the cycles at Allen and Kingston.
Kingston Steam Plant
The third plant from which samples were obtained was the Kingston
Plant. Samples were obtained from June 26 to December 18, 1979. Again,
intake water quality was analyzed for a number of pertinant parameters by
the TVA laboratory (Table 6).
TABLE 6. RAW WATER QUALITY AT THE KINGSTON STEAM PLANT
Parameter
Maximum
Minimum Median
Mean
pH, Std. Units
Total Suspended Solids
Total Organic Carbon,
Ammonia (field), mg/1
Ammonia (lab) , mg/1
Organic Nitrogen, mg/1
Chlorine Concentration
Chlorine Demand, mg/1
, mg/1
mg/1
> mg/la
8
15
4
0
0
0
1
0
.0
.0
.1
.03
.04
.22
.13
.47
6
9
2
0
0
0
0
0
.9
.0
.0
.01
.01
.10
.79
.19
7
12
2
0
0
0
1
0
.5
.0
.4
.02
.02
.13
.04
.27
_
12
2
0
0
0
0
0
.0
.7
.02
.03
.15
.99
.30
Calculation for chlorine concentration is:
After 10 minutes.
Feed Rate lb/24 hrs R. 90 _ ,,
-=•= =—- ' , .— x oj.22 - mg/1.
Flow Rate gal/min 6
15
-------
Cooling water flows for the generating unit sampled ranged from
103,364 gpm to 111,396 gpm with a mean of 106,294 gpm. Loads of this
unit correspondingly ranged from 111 to 132 MW with an average of 124 MW.
The chlorination cycle at the Kingston Plant is 30 minutes for each unit.
A comparison of the plants shows that pH is the only parameter for
which there was substantial consistency. The highest value of 8.0 units
was measured at Kingston, while the lowest was 7.1 at Allen. The Shawnee
Plant, located on the Ohio River, exhibited the highest suspended solids
concentration at 39 mg/1. High levels of both organic carbon and ammonia
nitrogen were observed at the Allen Plant. The combination of these com-
ponents apparently caused the observed median chlorine demand of 0.46 mg/1
to be significantly higher at Allen than at either of the other two plants,
16
-------
CHAPTER VII.
DESCRIPTION 01 ANALYTICAL PROCEDURES, SAMPLE PREPARATION,
AND SAMPLE HANDLING PROCEDURES
Precursors
This class of compounds includes the species which are available in
the inlet streams and are postulated to serve as the substrates for chlori-
nation, resulting in the formation of halogenated low molecular weight
halocarbons. The organic compounds determined in this class include poly-
hydroxybenzenes, amino acids, and humic and fulvic acids. Also determined
were the levels of Br , NHs and the natural color of the inlet water
samples.
The procedures developed and applied for the determination of these
precursors are outlined below.11
Determination of Natural Color. The platinum-cobalt method normally
used for the determination of color in natural water is based on a visual
comparison between standard chloroplatinate solutions and the sample.12
Because of the unavoidable variability inherent in making such compari-
sons, the method employed in this study used spectrophotometric measure-
ment of the absorbance of each sample at 362 nm as the means of comparing
samples to standard chloroplatinate solutions. As natural color depends
to some extent on pH, all samples were adjusted (if necessary) and
measured at a ph of 7.0 units. A Gary 118 Spectrophotometer and 1 cm
silica cells were used to measure the color. Standards were prepared by
dilution of a stock solution containing 1.0 g CoCl2'6^0+1.264 g ^PtClg
(1000 mg Pt) in 1000 ml pH=5 acetate buffer. Standards were prepared over
the range 5-70 mg Pt/1 in 5 mg Pt increments. Because of the nonlinearity
of the spectrophotometer1s response over this concentration range, these
data were segmented into several linear portions, and separate standard
curves were determined for each corresponding concentration range as
follows:
mg Pt/1
1-20
20-30
35-50
Intercept
+0.13821
-8.5930
-1894.3122
Corr. Coeff.
0.99954
0.99934
0.96710
17
-------
Determination of NHs. The quantitation of ammonia was performed
using a specific ion electrode which permits the rapid, low-level determi-
nation of NHs with few problems from chemical interferences or the color
and turbidity of the samples.13 Each sample was perserved with H2S04 upon
collection and stored at 4°C until analyzed as follows:
Reagents: 10 N NaOH ionic strength adjustment buffer (ISAB)
Distilled water
0.1 M NH4C1
Equipment: 1 Orion Model 401 Specific Ion Meter
1 HNU ISE-10-10-00 ammonia selective electrode
Procedure: The "liter-beaker" method was used to calibrate the
meter over the range 8.5-85.0 pg/1. Samples were
prepared by adding 1 ml ISAB/100 ml sample; and read-
ings were obtained immediately after calibration,
allowing 20-30 seconds for the electrode to equilibrate.
Any samples which read above 85.0 (Jg/1 were reanalyzed
after calibration of the meter over the appropriate
concentration decade. (Calibration should be repeated
after every 4-5 samples, or every 15 minutes.)
Standards were prepared by dilution of the NBLjCl stock solution, and a
standard curve derived from them. However, because of the non-linearity
of this curve at low concentrations, only the "liter-beaker" calibration
procedure was used to quantitate samples below 850 [Jg NHs/1.
Determination of Br . Inorganic bromide was determined using a bro-
mide ion selective electrode. The analytical procedure does not require
any sample pretreatment and permits the rapid low-level quantitation of
Br with few interferences.14 Each sample was analyzed as described below:
Reagents: 5 N NaN03 (ISAB)
Distilled water
0.1 N NaBr
Equipment: 1 Orion Model 401 Specific Ion Meter
1 HNU ISE-30-35-00 Bromide Selective Electrode
1 Orion (Model 09-02) Double Junction Reference Electrode
Procedure: The "liter-beaker" method was used to calibrate the
meter over the range 40-400 |Jg/l. Samples were pre-
pared by adding 2 ml ISAB/100 ml sample, and each
reading was made after allowing 30 seconds for equi-
libration. The meter was initially calibrated over
the range 40-400 [Jg/1. Any samples which read outside
this range were reanalyzed after calibration of the
meter over the appropriate range. To correct for drift,
the meter was recalibrated after every 4-5 samples, or
every 15 minutes.
Standards were prepared by dilution of the 0.1 M NaBr standard solution
and used to prepare a standard curve. Because of the non-linearity of
18
-------
this curve at low concentrations, the "liter-beaker" method was used
to calibrate the specific ion meter in order to obtain values below
800 |Jg Br~/l.
Determination of Humic and Fulvic Acids. Humic and fulvic acids
were extracted and concentrated from aqueous samples by adsorption of
these materials on polymeric resin. These materials are distinguished
primarily by the molecular weight ranges which they encompass and dif-
ferences in their solubilities in dilute mineral acids.15 Beyond these
characterizations, humic and fulvic materials have not been well defined.
However, their interactions with polymeric adsorbents such as Amberlite
XAD-2 are such that these humic and fulvic acids may be sequentially
eluted and thereby separated using such organic polymers.
Prepurified XAD-2 resin beads (Supelco Cat. No. 2-0279) were further
purified by 24-hour soxhlet extraction with acetone. This material was
then packed into glass columns of 0.9 cm id. and washed with 10 bed
volumes of 0.1 N NaOH and 10-bed volumes of deionized HgO. A bed height
.of 8.9 cm was used for these columns, which resulted in resin bed volumes
of 5.6 ml. This bed length was chosen because bed height vs cross-
sectional area ratios greater than 14:1 reportedly results in poor adsorp-
tion efficiencies.16 The procedures used for the determination of humic
and fulvic acids were as follows:
Reagents: 1 N NB^OH in methanol
Equipment: Gary 118 Spectrophotometer
Procedure: A 500 ml aliquot of each sample was adjusted to pH of
2 with HC1, and then was passed through the XAD-2 resin
column at a flow of <3.3 ml/min. (35 bed volumes/hr.)
This flow allowed the humic materials to be efficiently
adsorbed while maximizing sample throughput. The
adsorbed fulvic acids were eluted with 40 ml of deion-
ized water at pH of 7 units, while the humic acids were
removed with 40 ml of 1.0 N NH40H in methanol. Each
fraction was collected, diluted to 50 ml with deionized
water, and quantitated at 300 nm.
Standards for humic and fulvic acids were isolated from commercially
available soil-derived humic materials (supplied by Aldrich Chemicals,
catalog number HI,675-2). Precipitated humic acids were removed by
filtration of a 1 gm/1 aqueous solution of this humic material which had
been acidified to a pH of 2 units with HC1. The remaining solution of
fulvic acids was lyophilized to ^10 ml, and desalted by gel filtration.
The desalted concentrate was then lyophilized to dryness. Elemental
analyses of the humic and fulvic acids obtained in this fashion are given
below and agree with those values reported in the literature.17
Percent Composition of Humic and Fulvic Acids
C H N 0 Ash
Humic
Fulvic
19
51.8
30.0
3.5
2.5
10.2
10.2
73.1
52.9
1.6
14.6
-------
Values for oxygen were determined by difference after correction for the
ash content. The ash value reported above for fulvic acid is considered
normal. However, to achieve such a low value required very careful
desalting to remove the large amount of inorganic salts resulting from
this method of isolation of fulvic acids.
Standard curves were constructed using aqueous solutions prepared
from the humic and fulvic acid standards. The slope and intercept values
from these curves are presented below and were used in the quantitation
of water samples examined in this study.
Slope Intercept Corr. Coeff.
Humic Acids 31.12 -2.70 0.99882
Fulvic Acids 61.56 1.91 0.99954
Determination of Polyhydroxybenzene. The well-known reaction of phe-
nolic compounds with FeCls to yield colored complexes was the basis for
the method of analysis of polyhydroxybenzenes in this study. A list of
the compounds which are included in this class of analytes is as follows:
Trihydroxybenzene
Tetrahydroxybenzene
Pentahydroxybenzene
Hexahydroxybenzene
Unfortunately, most of these compounds are not commercially available.
However, because of the ease with which these compounds are oxidized,
it is unlikely that many of these compounds would persist in the environ-
ment and therefore would not exist as the polyhydroxybenzenes in the
aqueous samples examined in this study.
These materials were to be determined as a class of compounds and
as such were not isolated as individual species prior to analysis.
However, humic materials would be expected to be a positive interference
in this analysis. Since humic and fulvic acids were being determined
separately in this study, a scheme was devised to eliminate these inter-
ferring compounds prior to the determination of the polyhydroxybenzenes.
The response of the individual members of this class of components
to FeCls varies significantly. As such, the response observed when
applying the class analysis to aqueous samples will depend upon which
polyhydroxybenzenes are present and at what concentration. A more precise
description of such materials would require a determination of the indivi-
dual polyhydroxybenzenes species; however, the effort was beyond the scope
of this study.
The procedures used for the determination of polyhydroxybenzenes are
as follows:
20
-------
Reagents: 1% FeCl3(aq).
Equipment: Bausch and Lomb Spectronic 20
Procedure: Samples were filtered in 10 ml aliquots through a
2 cm column of Bio Gel P-2, followed by 20 mis of
0.1 N HC1. The polyhydroxybenzenes are contained in
the last 10 mis, which are treated with 4 drops of
Feds solution and quantitated at 500 nm.
Standard solutions were prepared from equimolar amounts of 1,2,4-trihydroxy-
benzene; 1,2,3,4-tetrahydroxybenzene; and hexahydroxybenzene. The benzene-
triol was obtained commercially (K and K Laboratories). However, the latter
two compounds were prepared using methods reported in the literature.18'19
The following slope and intercept values were obtained from the curve derived
from these standard solutions:
Intercept Corr. Coeff.
Polyhydroxybenzenes 30.27 0.59 0.9976
Determination of Amino Acids. The analysis of these compounds
was performed using the procedures described below:
Reagents: 0.1 N HC1
Equipment: Thermovac FD-l-DG Freeze Dryer
Procedure: A 500 ml aliquot of each water sample is placed in a
7000 ml round bottom flask and freeze dried to approxi-
mately 50 ml. The concentrated sample is then trans-
ferred to a 100 ml flask followed by a 5 ml rinse with
0.1 N HC1, and 100 ml of deionized water. Each sample
is then freeze dried to dryness, and shipped to the
analytical laboratory. Prior to analysis, each freeze-
dried sample was dissolved in 2 ml of pH 2.2 sodium
citrate buffer and spiked with 25 nM/ml each of nor-
leucine and
-------
For NHs and Br analyses, these spiked solutions were used to calibrate
the instrument before and during the analysis, and as such no data were
generated.
However, for all other analyses, spiked samples were processed
and their concentrations determined using the appropriate procedure.
Blank samples were also analyzed for each method and consisted of the
trip blanks discussed under Sampling Methods. Laboratory blanks were
analyzed only if the trip blanks gave values significantly greater than
the detection limit of the method.
Standard curves were prepared for at least seven different standard
concentrations. Detection limits were determined using the method of
Hubaux and Vos,20 and established as the minimum response which might
be due (within the 95 percent confidence interval) to a sample of zero
analyte content.
Halogenated Organics
Determination of Volatiles.21 Purge and trap techniques were utilized
for the analysis of the volatile halogenated organics. These techniques
consisted of purging a known volume of the aqueous sample with inert gas
and trapping the evolved volatile organics on a Tenax trap. Trapped
organics were eluted onto the head of a gas chromatographic (GC) column,
separated, and measured with an electrolytic conductivity detector. Purge-
and-trap and GC conditions for this procedure are given in Table 7. The
general procedures are outlined below:
TABLE 7. PURGE-AND-TRAP AND GC PARAMETERS
FOR VOLATILE HALOGENATED ORGANICS
Purge Gas
Purge Time
Purge Rate
Purge Temperature
Desorption Time
Desorption Temperature
GC Carrier Gas
Carrier Gas Flow Rate
CG Column Dimensions
GC Column Packing
GC Column Temperature Program
GC Detection
He
12 min
60 ml/min
20-25°C
7 min
180°C
He
30 ml/min
6 ft x 2 mm id
0.1% SP-1000 on Carbopack C
60°C to 220°C at 8°C/min and
20 min at 220°C
Electrolytic conductivity
22
-------
Equipment: Chemical Data Systems 310 Concentrator and Tracor
Model 560 Gas Chromatograph with Model 700 Hall
Detector
Procedure: A 10 to 20 ml aliquot of each sample was placed in
the CDS 310 concentrator. The sample was purged for
12 minutes with helium and the evolved organics
trapped on the Tenax trap. The trap was heated for
seven minutes at 180°C and the analytes flashed onto
the GC column, separated, and measured using an
electrolytic conductivity detector.
Determination of Semivolatiles.22,23,24 The semivolatile constituents
were divided into two groups and analyzed accordingly. The acidic (phenols)
components were determined by acid adjustment of the pH, methylene chloride
extraction, and gas chromatograph analysis using electron capture detection.
The base neutral species were analyzed using the same method except the
sample aliquot was made alkaline before methylene chloride extraction.
Extraction and sample preparation procedures were as follows:
Equipment: Hewlett-Packard Model 5840A GC/ECD.
Procedure: Adjust the pH of 1000 ml sample to approximately 2
units with ^864 and extract with 3 x 60 ml of CH2C12-
The combined extract is dried over MgS04, decanted
off, and reduced in volume to 1 ml in a Kuderna-Danish
apparatus. Each sample was then "solvent exchanged"
by adding 5 ml hexane and again reducing in volume
to 1 ml.
Acidic semivolatile compounds, including phenols, were analyzed with
a 1 percent SP-1240 DA column. The deactivation process used while pre-
paring this column packing decreases adsorption of phenols onto the packing,
thus eliminating the need for derivatization of these compounds.
Gas chromatographic conditions are summarized in Table 8 below.
TABLE 8. GC-MS PARAMETERS FOR ACIDIC
SEMIVOLATILE HALOGENATED ORGANICS
Column Dimension 6 ft x 0.2 mm
Column Material 1% SP-1240 DA
Carrier Gas 5% Methane and 95% Argon
Carrier Gas Flow Rate 60 ml/min
Temperature Program 80°C to 200°C at 8°C/min and
2 rain at 200°C
Detector Electron Capture Ni63
23
-------
Base-neutral semivolatile compounds were determined by GC-ECD using
a 3 percent SP-2250 DB column. Gas chromatographic conditions are
summarized in Table 9.
TABLE 9. GC-ECD PARAMETERS FOR NEUTRAL
SEMIVOLATILE HALOGENATED ORGANICS
Column Dimension 6 ft x 2 mm
Column Packing 3% SP-2250 DB
Carrier Gas 5% Methane/95% Argon
Flow Rate 60 ml/min
Temperature Program 60°C to 270°C at 5°C/min
Quality Assurance. Accuracy and precision of the volatile and semi-
volatile analytical methods were determined through the analysis of stand-
ard reference, blank, and spiked samples which were examined periodically
during this study. Quality control samples were prepared and analyzed
with each group of samples. In the case of the volatile compound analysis,
trip blanks were also examined. Detection limits were determined from
the analysis of spiked samples and established at those levels where such
analysis proved satisfactory. The quality control program is described
in more detail in Appendix C. Actual data are presented there.
LABORATORY BRANCH
DIVISION OF NATURAL RESOURCES SERVICES
SAMPLE HANDLING PROCEDURES FOR ORGANIC ANALYSIS -
CHLORINATION STUDIES
I. Containers
A. Containers for Volatile Organics
1. 40-ml scr'ew cap glass vials equipped with Teflon-faced
silicon rubber septa and open top screw caps; Pierce
Chemical Company, catalog numbers 13075, 12722, and
13219, or equivalent.
B. Containers for Semivoltile Organics
1. One-gallon amber solvent bottles with Teflon-lined caps.
II. Container Preparation
The Laboratory Branch furnished precleaned containers prepared as
follows:
24
-------
A. Containers for Volatile Organics
I. Wash the 40-ml vials, Teflon septa, and caps with hot
detergent water.
2. Thoroughly rinse with tap water.
3. Thoroughly rinse with reagent water.
4. Heat the containers and septa in an oven at 105°C for one
hour.
5. Cool to room temperature in an desiccator charged with
silica gel.
B. Containers for Semivolatile Organics
1. Wash the 1-gallon amber solvent bottles and Teflon-lined
caps with hot detergent water.
2. Thoroughly rinse with hot tap water
3. Thoroughly rinse with reagent water.
4. Seal with Teflon-lined caps.
5. Bottles must not be opened until just prior to filling with
sample or blank water.
III. Sample Collection - If the sampling line is not continuous flow, allow
discharge to flow several minutes before sampling.
A. Volatile Organics
1. Collect two 40-ml vials each time samples are collected.
2. Collect samples by slowly filling the vial just to over-
flowing (a convex meniscus is the desired stopping point).
Avoid introducing air bubbles into the sample.
3. Using spatula, carefully add one sodium thiosulfate granule
(about 3 mg) to each filled vial.
4. Using clean forceps, place the septum (Teflon side down) on
the sample meniscus and seal the bottle with the screw cap.
5. Invert vial and lightly tap the lid on a solid surface to
ensure that the sample has been properly sealed. The
absence of entrapped air bubbles indicates a proper seal.
If any bubbles are present, open the vial, add additional
sample and reseal. Shake gently to ensure solubilization
of thiosulfate crystal.
25
-------
6. Wrap the vials in waterproof packing material, place in
ice chest, cover with ice, and seal the chest.
B. Semivolatile Organics
1. Fill a 1-gallon bottle to the narrow neck with a
representative sample.
2. Do not allow fingers to come in contact with the inside
of caps or bottles.
3. Seal bottle with Teflon-lined caps and place in ice chest.
4. Place padding between bottles to prevent breakage.
5. Cover the sample bottles with crushed ice and seal the
ice chest.
IV. Sample Identification
All samples and blanks must be accurately identified with a sample
number using waterproof labels and waterproof ink. Field worksheets
(form TVA 17057) must be completed including sample number, date
and time of sampling, type of sample and sampling site. The field
sheets should be signed by the collector and the original attached
to the outside of the ice chest. A copy of the field sheet is
retained by the collector as a record of sample collection.
V. Sample Delivery
Samples sould be delivered to the Laboratory Branch within 24 hours
after collection. Samples must be analyzed within 14 days of col-
lection.21 Samples not meeting this criteria will be considered
unacceptable. If recollection is impossible, data from older samples
must be qualified in the laboratory report.
26
-------
CHAPTER VIII.
STATISTICAL ANALYSIS
This section presents the methodology used to analyze the data rather
than that used to analyze the samples. Water quality analyses were per-
formed according to Standard Methods for the Analysis of Water and Waste-
water (14th Edition) or according to currently accepted EPA procedures.
With regards to precursors, where a method had to be adapted from the
literature or was a nonstandard method, an extensive methodology develop-
ment and quality control program was followed.25
Nevertheless, the error inherent in the precusors analyses influenced
the interpretation of statistical procedures as noted below. Replicate
samples were analyzed by two different laboratories using comparable or
similar procedures for the halogenated organic compounds. In some cases,
variations were noted which were attributed primarily to sample contamina-
tion during transport and secondarily, to the fact that some of the com-
pounds of interest, particularly methylene chloride, are commonly used
industrial and laboratory solvents. Their contamination of GC supply
gases and the laboratory atmosphere makes it extremely difficult to con-
sistently achieve sub-part per billion detection limits on water samples.
Battelle-Columbus Laboratories analyzed 30 samples for halogenated
organics to validate the sampling and analytical methodology used by TVA.
The Battelle halogenated organics data base was not used as part of the
general data base for the statistical analysis.
The TVA data base used in the study consisted of multiple sets of
volatile halogenated organic analyses for each plant. Generally, eight
samples per sampling date were analyzed:
Intake prior to a chlorination cycle
Intake following chlorination
Inlet 5 minutes after the start of chlorination
• Outlet 5-20 minutes into chlorination* (Outlet 1)
• Outlet 10-40 minutes into chlorination** (Outlet 2)
Outlet after completion of a chlorination cycle (Outlet 3)
Trip blank-organic free water transported from the lab to the site
and back and analyzed to determine transportation contamination
Lab blank-organic free water taken through the analysis procedure.
The number of sampling dates for the volatile organics varied from
plant to plant. The Allen plant was sampled a total of nine times between
the dates of June 5 and December 11, 1979. The Kingston plant was sam-
pled eight times between June 26 and December 18, 1979. Samples were
taken at Shawnee on six occasions between June 12 and November 6, 1979.
For the precursors the data base was not as extensive. Precursors
shown in Table 2 as being monitored by TVA were analyzed approximately as
*Exact times varied from 5 to 20 minutes depending on the plant.
**Times varied from 10 to 40 minutes depending on the plant.
27
-------
frequently as the halogenated organic compounds. Data provided by Battelle
were available as follows:
Allen 5 dates August 21 to December 11
Kingston 5 dates August 21 to December 18
Shawnee 2 dates October 2 and November 6
These differences are noted because they affected the statistical analysis.
The organic compounds and precursors were coded, keypunched, and
organized as separate computer files to maximize flexibility. Any subset
of either file could be selected and combined into a merged file for pro-
cessing. Data could be accessed by parameter, by plant, by date, by
sample location or other criteria to provide the merged data set.
Prior to performing any of the hypothesis testing, the data were
examined for statistical characteristics. First, a frequency distribution
of values above and below the analytical detection limit was generated.
Compounds detected less frequently than 70 percent at any location were
deleted from further consideration due to the severe limitations this
placed on the statistical tests.
Many of the halogenated organic compounds existed in concentrations
below detection limits. For data analysis, these data were not considered.
Consequently, the mean, median, and minimum concentrations are often
higher than would be the case if detection limit or half the detection
limit were used for these concentrations. Also, the standard error and
standard deviation are smaller than otherwise. The effect of omitting
these concentrations is not as pronounced in the analysis of the precur-
sors with chloroform because relatively few chloroform concentrations
occurred below detection limits.
DESCRIPTIVE STATISTICS
Allen Steam Plant
Halogenated Organic Compounds. The frequency tabulations showed that
for this plant, six volatile halogenated compounds were detected and had
the distribution shown in Table 10. With the exception of chloroform and
1,1,1-trichloroethane, the compounds did not meet the criterion of a
70 percent detection frequency.
The descriptive statistics were also informative in establishing
which of the compounds should be tested further. The means, maximum, mini-
mum, and median are shown in Table 11. Chloroform and bromodichloromethane
concentrations appeared to be influenced by cooling system chlorination.
Only chloroform was selected for further statistical hypothesis testing.
28
-------
TABLE 10. HALOGENATED ORGANIC COMPOUND DETECTION FREQUENCY SUMMARY - ALLEN PLANT
Compound
Bromodichlorome thane
Dibromochlorome thane
Trans- 1 , 2-dichloroethylene
1 ,2-dichloroethane
1 , 1 , 1-trichloroethane
Chloroform
Intake (b)
11.1
22.2
11.1
55.6
88.9
100.0
Detection Frequency
Inlet Outlet 1
77.8
44.4
0
44.4
88.9
100.0
77.8
55.6
0
22.2
88.9
100.0
, Percent*^
Outlet 2
77.8
55.6
0
33.3
88.9
100.0
Outlet 3(c)
11.1
22.2
0
33.3
88.9
100.0
Average
51.1
40.0
2.2
37.8
88.9
100.0
based on nine samples analyzed at each location, detection limit is 0.05
prior to start of chlorination
(c)
after cessation of chlorination
-------
TABLE 11. HALOGENATED ORGANIC COMPOUND DESCRIPTIVE STATISTICS - ALLEN PLANT
(a)
Compound
Bromodichlorome thane
Dibromochlorome thane
Trans-1 ,2-dichloro-
ethylene
1 ,2-dichloroethane
1,1, 1-trichloroethane
Chloroform
data exclude less
mean
maximum
minimum
median
(d)
mean
mean
maximum
minimum
median
(d)
mean
mean
maximum
minimum
A- (e)
median
(d)
mean
mean
maximum
minimum
median
(d)
mean
mean
maximum
minimum
median
(d)
mean
mean
maximum
minimum
median
(d)
mean
than detection
Intake
0.30
0.30
0.30
<0.05
0.06
0.75
1.00
0.50
<0.05
0.19
0.06
0.06
0.06
<0.05
0.03
0.13
0.20
0.07
<0.05
0.08
0.99
2.00
0.10
0.25
0.88
0.53
2.90
0.05
0.09
0.53
Inlet
1.01
2.10
0.40
0.40
0.79
0.80
1.50
0.30
<0.05
0.37
No values
above
detection
<0.05
0.025
0.23
0.30
0.20
<0.05
0.11
1.40
3.20
0.50
1.00
1.25
5.74
10.00
0.40
5.00
5.74
values except as noted
Outlet 1
1.23
3.00
0.50
0.50
0.96
0.66
1.50
0.10
0.25
0.38
No values
above
detection
<0.05
0.025
0.15
0.20
0.10
<0.05
0.05
1.11
1.80
0.40
0.90
0.99
5.82
11.00
0.40
5.15
5.82
; all values
Outlet 2
1.29
3.10
0.40
0.65
1.01
0.62
1.00
0.20
0.20
0.36
No values
above
detection
<0.05
0.025
0.17
0.20
0.10
<0.05
0.07
1.19
3.00
0.40
0.80
1.06
6.63
11.00
0.40
6.25
6.63
are expressed
Outlet 3('
0.90
0.90
0.90
<0.05
0.12
0.90
1.00
0.80
<0.05
0.22
No values
above
detection
<0.05
0.025
0.13
0.20
0.10
<0.05
0.06
1.33
2.00
0.50
1.05
1.18
0.77
4.40
0.20
0.25
0.77
as pg/1
prior to chlorination
( c}
after the cessation of chlorination
(d)
(e)
mean of all data where less than detection values are set equal to DL/2
all data.
30
-------
Precursors. Detection frequencies for water quality data and precur-
sors (bromide, pH, substrate) were not calculated because there were no
cases where the detection frequencies percentages were less than 100
percent.
The descriptive statistics are shown in Table 12. In comparison with
the other plants the chlorine dosage, substrate concentrations, and
temperatures are more favorable to chloroform production. Free residual
chlorine, nitrogen species, and bromide are less favorable assuming the
proposed mechanistic hypothesis is accurate.
Kingston Steam Plant
Halogenated Organic Compounds. Table 13 shows the detection frequen-
cies for this plant. Only five volatile halogenated compounds were
detected of 21 measured. They were Bromodichloromethane, Dibromochlori-
methane, Methylene Chloride, 1,1,1-Trichloroethane, and Chloroform.
Methylene chloride was occasionally found while trans-l,2-dichloroethylene
and 1,2-dichloroethane were not. Of the five compounds, only chloroform
was detected more frequently than 70 percent at all locations and times.
Bromodichloromethane was detected with better than 70 percent frequency
at the inlet and the outlet during chlorination.
The descriptive statistics for Kingston are similar to those for Allen
(Table 14). Chloroform concentration appears to have a definite relation-
ship with cooling system chlorination while bromodichloromethane and
1,1,1-trichloroethane potentially are related to chlorination.
The mean and maximum chloroform concentrations at Kingston are lower
than those at Allen for the inlet, outlet 1, and outlet 2 samples. This
may be due to the fact that the chlorine dosages at Allen were higher.
This relationship is discussed later in this section of the report.
Another trend apparent in the data was the difference between compounds
with respect to the frequency of detection and the mean concentration at
various locations within the system. Chloroform and bromodichloromethane,
two of the trihalomethanes, behaved similarly. Concentrations at the
intake were generally low indicating that only traces of these compounds
were entering the plants from upstream sources. Concentrations also
decreased rapidly after chlorination cycle completion indicating that the
reaction is very dependent on the chlorine residual concentration.
The behavior of 1,1,1-trichloroethane was different than that of
chloroform and bromodichloromethane. Concentrations at the intake were
generally lower than elsewhere in the system, but following chlorination
the concentration at the outlet was maintained at a level only slightly
lower than during chlorination.
Possibly these differences in the behavior of specific compounds are
explainable on the basis of different reaction mechanisms and/or different
substrates.26
31
-------
TABLE 12. PRECURSORS - DESCRIPTIVE STATISTICS - ALLEN PLANT
(a)
Parameter
Chlorine Dosage, mg/1
pH, standard units
Bromide, |Jg/l
Nitrogen Species, pg/1
Free Residual Chlorine, mg/1
Total Residual Chlorine, mg/1
Substrate, mg/1
Intake Temperature , °F
Inlet Temperature, °F
Outlet Temperature, °F
Mean
1.23
-
278.12
459.94
0.17
0.40
2.12
73.58
72.80
86.68
Minimum
0.80
7.10
95.80
266.20
0.09
0.16
0.70
51.80
46.00
54.00
Maximum
2.10
7.70
670.00
728.10
0.23
0.65
3.00
87.60
87.60
100.00
1.96 Sigma Limits
About the Mean
0.89 to 1.57
7.22 to 7.51
14.33 to 570.57
319.40 to 600.49
0.13 to 0.21
0.28 to 0.53
1.02 to 3.22
64.68 to 82.48
62.72 to 82.88
75.48 to 97.87
Lo
K3
(a)
Values measured at intake except chlorine residuals at inlet and temperature as noted.
-------
TABLE 13. HALOGENATED ORGANIC COMPOUND DETECTION FREQUENCY SUMMARY - KINGSTON PLANT
Compound
Bromodichloromethane
Dibromochlorome thane
Methylene Chloride
1 , 1 , 1-trichloroethane
Chloroform
Intake (b)
12.5
0
12.5
37.5
75.0
(a)
Detection Frequency, Percent
Inlet Outlet 1 Outlet 2
100.0
12.5
12.5
50.0
100.0
100.0
25.0
12.5
50.0
100.0
87.5
25.0
12.5
50.0
100.0
Outlet 3^
0
0
12.5
37.5
75.0
Average
60.0
12.5
12.5
45.0
90.0
Abased on eight samples analyzed at each location, detection limit is 0.05 [Jg/1
prior to start of chlorination
fc")
after cessation of chlorination
-------
TABLE 14. HALOGENATED ORGANIC COMPOUND DESCRIPTIVE STATISTICS - KINGSTON PLANT
Compound
Bromodichloromethane
Dibromochlorome thane
Methylene chloride
1,1, 1-trichloroethane
Chloroform
mean
maximum
minimum
Cd)
mean
mean
maximum
minimum
(d)
mean
mean
maximum
minimum
fd)
mean
mean
maximum
minimum
fd)
mean
mean
maximum
minimum
(d)
mean
Intake (b)
0.40
0.40
0.40
0.07
no
values
above
0.025
1.10
1.10
1.10
0.16
0.17
0.20
0.10
0.08
0.14
0.30
0.07
0.11
Inlet
0.44
0.60
0.30
0.44
0.08
0.08
0.08
0.03
60.00(e)
60.00
60.00
7.52
0.48
0.70
0.30
0.25
3.83
6.30
2.10
3.83
Outlet 1
0.65
1.00
0.40
0.65
0.49
0.90
0.08
0.14
I6.00(e)
16.00
16.00
2.02
0.40
0.60
0.20
0.21
4.76
7.20
3.00
4.76
Outlet 2
0.73
0.60
1.00
0.64
0.09
0.09
0.08
0.04
5.00
5.00
5.00
0.65
0.38
0.60
0.20
0.20
4.45
5.40
3.60
4.45
Outlet 3^
no
values
above detection
0.025
no
values
above detection
0.025
30. 00^
30.00
30.00
3.77
0.37
0.80
0.10
0.15
0.18
0.40
0.10
0.14
(a)
(b)
(c)
(d)
(e)
data exclude values less than detection except as noted; all values are |Jg/l
prior to chlorination
after the cessation of chlorination
mean of all data where less than detection values are set equal to DL/2
data point outside the 95 percent confidence interval when less than detection values are included;
suspected contamination.
-------
Precursors. The precursor data summary for this plant shows that
with respect to bromide and nitrogen species, the formation of trihalo-
methanes is favored (Table 15). However, the chlorine dosage and the
substrate concentrations were less conducive to trihalomethane production.
Shawnee Steam Plant
The data base for this plant was more limited than that for the other
two plants. Comparisons between the Shawnee data and that of the other
plants should be made with caution.
Halogenated Organic Compounds. The detection frequency summary for
this plant shows that only chloroform was detected in a manner consistent
with the other plants (Table 16). The other compound detected with greater
than 70 percent frequency at all locations was 1,2-dichloroethane. While
this compound was detected irregularly at the Allen Plant, and never at
Kingston, Shawnee detection frequencies were never less than 100 percent.
Why the difference for this particular compound was observed is unclear,
however, the mean concentrations are indicative of only a mild plant
related effect (Table 17). This compound was not subjected to further
analysis.
Concentrations of bromodichloromethane where the values were initially
low, increased substantially during chlorination, then rapidly dropped to
low levels again. It is also interesting that formation of the dibromo
compound was higher at the plants having the highest and lowest bromide
ion concentrations, namely, Allen and Shawnee. This suggests that bromide
ion concentration is not related to production of dibromochloromethane in
a simple way.
Precursors. The data summary for precursors at this plant is shown
in Table 18. Relative to the other plants the chlorine dosages were the
lowest, yet the chloroform concentrations were the highest. This is proba-
bly due to interaction effects with the other variables, particularly
bromide ion and nitrogen species. Shawnee also had relatively high tempera-
ture compared to Kingston which had both the lowest temperatures and the
lowest chloroform concentrations.
STATISTICAL TESTS
The statistical analysis was performed using the Statistical Package
for Social Sciences (SPSS).27 Details of the procedures are available in
this reference and standard statistical texts. Brief summaries of the
tests are given below.
The data on the organic compounds were first screened to determine
locations where detailed analyses would be done and for which compounds.
The most frequently detected compound was then used for subsequent tests.
Three basic procedures were used to test various hypotheses about the
relationships.
35
-------
TABLE 15. PRECURSORS - DESCRIPTIVE STATISTICS - KINGSTON PLANT
(a)
Parameter
Chlorine Dosage, mg/1
pH, standard units
Bromide, (JgA
Nitrogen Species, |Jg/l
Free Residual Chlorine, mg/1
Total Residual Chlorine, mg/1
Substrate, mg/1
Intake Temperature , °F
Inlet Temperature, °F
Outlet Temperature, °F
Mean
0.88
-
133.33
173.24
0.42
0.65
1.58
62.77
64.29
80.43
Minimum
0.60
7.00
112.00
100.00
0.06
0.32
0.90
46.40
46.00
61.00
Maximum
1.13
8.00
172.00
257.20
1.12
1.61
2.70
70.00
73.00
88.00
1.96 Sigma Limits
About the Mean
0.70 to 1.05
7.20 to 7.77
50.00 to 216.67
103.20 to 243.28
0.14 to 0.69
0.29 to 1.00
0.67 to 2.49
53.85 to 71.70
54.43 to 74.12
69.05 to 91.80
(a)
Values measured at intake except chlorine residuals at inlet and temperature as noted.
-------
TABLE 16. HALOGENATED ORGANIC COMPOUND DETECTION FREQUENCY SUMMARY - SHAWNEE PLANT
u>
Compound
Bromodichlorome thane
Dibromochlorome thane
Trans-l,2-dichloroethylene
1 , 2-dichloroethane
1,1, 1-trichloroethane
Chloroform
Intake (b)
0
50.0
16.7
100.0
50.0
100.0
Detection Frequency,
Inlet*-0) Outlet 1
80.0
60.0
0
100.0
60.0
100.0
100.0
66.7
16.7
100.0
33.3
100.0
Percent ^
Outlet 2
100.0
66.7
0
100.0
33.3
100.0
Outlet 3
0
33.3
0
100.0
50.0
100.0
Average
55.2
55.2
6.8
100.0
44.8
100.0
(a)
(b)
(c)
(d)
(e)
based on six samples analyzed at each location except inlet
prior to start of chlorination
based on five samples
after cessation of chlorination
weighted to reflect fewer number of samples at inlet
-------
TABLE 17. HALOGENATED ORGANIC COMPOUND DESCRIPTIVE STATISTICS - SHAWNEE PLANT
(a)
co
oo
Compound
Bromodichlorome thane
Dibromochloromethane
Trans 1,2-dichloroethane
1 , 2-dichlorethane
1,1, 1-trichloroethane
Chloroform
mean
maximum
minimum
(d)
mean
mean
maximum
minimum
(d)
mean
mean
maximum
minimum
(d)
mean
mean
maximum
minimum
(d)
mean
mean
maximum
minimum
(d)
mean
mean
maximum
minimum
mean
Intake (b)
no values
above
detection
0.025
0.13
0.20
0.08
0.08
0.08
0.08
0.08
0.03
5.03
7.50
2.60
5.03
1.10
3.00
0.10
0.56
0.30
0.50
0.08
0.25
Inlet Outlet 1
0.84
1.80
0.10
0.84
0.28
0.40
0.10
0.21
no values
above
detection
0.025
6.68
9.00
4.60
6.68
1.30
3.40
0.20
0.79
7.86
13.60
5.00
7.86
1.13
2.20
0.40
1.13
0.30
0.40
0.20
0.21
0.20
0.20
0.20
0.05
6.28
13.00
2.70
6.28
1.90
3.60
0.20
0.65
9.90
18.00
4.80
9.90
Outlet 2
1.10
2.40
0.40
1.10
0.30
0.50
0.20
0.21
no values
above
detection
0.025
6.48
13.00
2.70
6.48
1.60
3.00
0.20
0.55
9.22
18.00
4.60
9.22
Outlet 3^
no values
above
detection
0.20
0.30
0.10
0.08
no values
above
detection
0.025
5.33
7.80
3.70
5.33
1.53
4.20
0.20
0.78
0.43
0.60
0.20
0.43
(a)
(b)
(c)
(d)
data include values less than detection except as noted; all values are |Jg/l
prior to chlorination
after the cessation of chlorination
mean of all data where less than detection values are set equal to DL 1/2
-------
TABLE 18. PRECURSORS - DESCRIPTIVE STATISTICS - SHAWNEE PLANT
(a)
u>
Parameter
Chlorine Dosage, mg/1
pH, standard units
Bromide, MgA(b) (b)
Nitrogen Species, |Jg/l
Free Residual Chlorine, mg/1
Total Residual Chlorine, mg/1
Substrate, mg/1
Intake Temperature, °F
Inlet Temperature, °F
Outlet Temperature, °F
Mean
0
107
186
0
0
1
71
75
86
.79
-
.20
.35
.31
.46
.85
.60
.17
.58
Minimum
0
7
46
150
0
0
1
60
60
73
.58
.30
.40
.90
.09
.25
.50
.80
.00
.50
Maximum
1
7
168
221
0
0
2
80
85
96
.04
.70
.00
.80
.56
.66
.20
.60
.00
.00
1.96 Sigma
About the
0
7
0
0
-2
64
65
78
.57
.24
.12
.26
.59
.04
.65
.29
to
to
to
to
to
to
to
to
Limits
Mean
1.
7.
0.
0.
6.
79.
84.
94.
00
56
51
66
30
16
68
88
(a)
(b)
Values measured at intake except chlorine residuals at inlet and temperature as noted.
Statistics based on only two analyses.
-------
This first hypothesis tested was whether there was a significant
change in the concentration of a particular halogenated compound as the
water passed from the intake to the outlet of a given plant cooling system.
Based on classical chemical kinetic theory and monitoring of free and total
residual chlorine in cooling systems, it was expected that chloroform con-
centrations would exhibit a clear cut trend with time and location in the
system. A simple examination of the data was performed by plotting loca-
tion on the abscissa and chloroform concentration on the ordinate. When
the data from a single sampling date are plotted they exhibit a character-
istic pattern known as an umbrella curve (Figure i).28>29 Concentrations
at the raw water intake were characteristically low, but increased markedly
at the inlet to the condenser after chlorine had been dosed into the system.
At the condenser outlet there was a further tendency toward increasing
chloroform concentrations as long as chlorine was still being added.
However, once chlorination ceased the concentrations quickly returned to
background levels.
When the data from all sampling dates were combined the resulting
envelope curve shows the influences of random and chemical influences on
chloroform yields (Figure 2). Plotting of concentration versus sampling
date at the inlet and outlet failed to result in an identifiable pattern
such as might be produced by seasonal differences in reactive substrate
material (Figures 3 and 4). This does not rule out the possibility that
such trends exist but may mean only that there are other factors involved
as well.
The hypothesis* that there was a significant increasing and then
decreasing trend was tested by means of nonparametric statistical proce-
dure as described below. Following this test, a multiple comparisons pro-
cedure was used to determine whether pairwise differences, i.e., between
any two locations, were significant and if so, at what confidence level.
Model:
y. . = u + L. + D. + E. .
yij H J i iJ
where Y.. = ppb chloroform at location j on day i
J
L. = effect due to location j
D. = effect due to day i
E. . = random error (effect of all other uncontrolled factors
"^ affecting chloroform concentration except location and
day) associated with measurement at location j on day i.**
''"This hypothesis was based on prior expectations of what occurs in a
chlorination cycle, rather than being based on the data at hand.
'-"Location" really is a combination of location and time (e.g., OUT 12
and OUT 24).
40
-------
:>1*TlS11t,AL ANALYSIS iYSTFtM
MCwTb=6 DAY-2 6
FtOT
16:46 THURSDAY, MAY 29, 1980 18
i_tGt,\0: * - r~0bi, B = 2 OBs7~bTCT~
A
4.3 +
4.2
4.1
4.0
3.9
3.e +
3.7 +
2.3 +
I 2.1 +
2.0
1.9
1.8 +
1.7 +
~1T5~
!.!>
l.i +
1.1 *
1 .O »
O.V +
0.6
0.7
0.6 +
0.5 *
0.4 +
0.3 +
O.i +
TRPOO
-+•
INTOO
~ LC C«T ION
INL12
OOT12
OUT35
I NT* 5
Figure 1. Chloroform - Concentration Versus Location
-------
12
11
10
9
C 8
H
L
0
R 7
0
R 6
-0 H
hO
P 5
P
B
t
3
2
1
0
NOTE
STATISTICAL ANALYSIS SYSTEM 10:47 TUESDAYt JUNE 3, 1980 17
PLOT OF CHLOROFO*LOC TIME LEGEND: A = 1 OBSt 8=2 OBSt ETC.
|
+
1 '
+ A A
1
+ B B
1
+ A
1
1 A
+ A
| A A
1
I *
+
|
1
+
1 *
1 A
| A A A
+ B
1 &
1 A
+
1
1
1
* A A
I A A
1 A
1
+
I
1
+
1 B
| A A C A A B A
f A 8 A F E
+ F C E C
LABOO TRPOO INTOO INL12 OUT12 OUT2* OUT35 INT*5
LOCATION AND TIME AFTER CHLORINATION
: 2 OBS HAD MISSING VALUES OR WERE OUT OF RANGE
Figure 2, Chloroform - Concentration Versus Location For Ail Data
-------
12 +
11
10
C 8
H
R 7
0
R 6
P 5
P
3
2
ALLEN STEAM PLANT
8:42 THURSDAY« JUNE 5t 1980
LOCATION AND TIME AFTER CHLORINATION=INL12
PLOT OF CHLOROFO*«ONTHDAY LEGEND: A = 1 OBS» B = 2 DBS, ETC.
06 05
06 19
07 10
08 07
08 21
09 25
10 16
MONTHDAY
Figure 3. Chloroform Versus Month/Day For Inlet 12 Minutes
11 27
12 11
-------
12 +
11
10
C 8
H
R 7
0
R 6
H
5
1
ALLEN STEAM PLANT
8:42 THURSDAY. JUNE 5, 1980 11
LOCATION AND TIME AFTER CHLORINATION=OUT12
PLOT OF CHLOROFO«MONTHDAY LEGEND: A = 1 OBS. B = 2 OBS. ETC.
06
06 19
07 10
08 07
08 21
69 25
10 16
11 27
12 11
MONTHDAY
Figure 4. Chloroform - Concentration Versus Month/Day For Outlet 12 Minutes
-------
Assume that the errors, E.., are all independent random variables
having the same (but arbitrary; continuous distribution. We want to test
initially the hypothesis:
Ho:Li = ...=15 (i.e., there is no true difference in chloroform
concentration at the various locations)
versus
Ha:Li £. . • £!•/£• • -^Ls, for some $., 1>£^5 (i.e., there is an increase
in chloroform concentration up to some location
(unknown); then (perhaps) a decline.
Procedure: (£ unknown procedure for block designs)
(1) Rank the observations for each day from smallest (rank 1)
to largest (rank 5) . Use average ranks if two or more
observations are tied.
(2) Sum the ranks assigned to each location. Estimate the
location with highest chloroform concentration values
corresponding to the largest sum of ranks.
(3) Count the number of pairs of observations increasing up to
the third location and also count the number of pairs
decreasing after the third location. (Used to determine
whether a significant up-down trend exists.)
(4) Standardize AS to get the test statistic Ap .
This is followed by the multiple comparisons test.30 The tests are
approximate .
Declare L. + L. if
R. - R.
-q(.05,5,oo) r"^'^]2 >18.30
Declare L. + L. if
(a = 0.05)
>
R. -
-q(.01,5,«>) [^
(a = 0.01)
With this procedure it is possible to test for differences between
two sets of data for continuous variables. The application to observed
chloroform concentrations at the intake, inlet, and outlet of each plant's
cooling system is described in the results.
The second hypothesis tested was that there was a relationship, not
necessarily causal, between the levels of organic compounds measured at
various points in the cooling system and certain of the precursors. The
problem was twofold. First, most of the organic compounds were not
45
-------
detected above the analytical threshold of 0.05 ppb. This meant that
there was no variation in the concentrations which could be matched against
variations in the precursors to test for a relationship. Second, the large
number of precursors would result in an astronomical number of combinations
if each one were tested individually. This problem is complicated by the
necessity of testing the precursors against each other to identify the
degree of correlation in the data set. Any inferences regarding causality
must be adjusted for possible side-effects of this nature.
The approach selected was to use existing mechanistic hypotheses
about the factors involved in the chlorination or bromination reaction
and concentrate on supporting or refuting them. Few studies have been
conducted on the factors affecting the levels of product compounds in
other than a completely controlled experiment and fewer still have been
attempted for a power plant system.
The present working hypothesis for the chlorination reaction involves
the attack of hypochlorous acid or hypochlorite anion on naturally occur-
ring humic and fulvic acids. This reaction is thought to be pH dependent
being favored at alkaline pH, possibly due to deprotonation of the hypo-
chlorous acid and/or the humic/fulvic acid complex and enhancement of mass
transport limited reaction kinetics.
The use of partial correlation analysis was selected for the following
reasons:
(1) both simple and complex relationships could be handled,
(2) the effects of confounding variables could be removed,
(3) the reduction in the number of degrees of freedom for each
partial correlation level was tolerable,
(4) the direction and strength of each relationship could be obtained
from the partial correlation coefficients,
(5) the significance levels of the correlation could be estimated
from t-tests of the hypothesis that the correlation coefficient
was significantly different from zero.27 Note: Due to correla-
tion effects the significance levels may be somewhat lower than
reported.
Following is a brief discussion of partial correlation analysis.
More complete treatment of the subject is given in Nie27 and Ostle.31
As mentioned above partial correlation provides a measure of the
association between two variables while simultaneously controlling for the
effects of one or more other variables. Partial correlation is based on
the assumption that the relationship between the control variable(s) and
both the independent and dependent variables is linear. While this may
seem like a stringent restriction, it is no more so than the attempt to
fit a linear multiple regression to untransformed data.
46
-------
Partial correlation coefficients may be considered as being constructed
by statistically calculating new dependent and independent variables with
the effects of the control variable (s) removed. This is done by predicting
(from the simple correlation coefficient) the dependent and independent
variables from the knowledge of the effects of the control variable. The
new variable is constructed by taking the difference between the actual
value of the original independent variable (for each observation) and its
value as predicted by the control variable. The new variables are not
correlated at all with any of the controls and therefore the correlation
represents the association with the confounding effects removed. However,
rather than actually calculating new variables, the computation can be
accomplished by using the iasic formula:
r.
r = i
rik rjk
where k is the index for the control variable, and i and j are, respec-
tively, the indices for the independent and dependent variables. Extension
to multiple control variables is relatively straightforward.
As with linear regression analysis, a partial correlation analysis
cannot distinguish between a nonexistent relationship and one which is
simply nonlinear. That is, a nonsignificant correlation coefficient
cannot be taken to mean that the variables in question are not related,
but only that no linear effect is observed.
The partial correlation coefficients were calculated for each of the
variables thought important in the reaction producing chloroform. Coeffi-
cients were calculated for each plant, each location, and each time indi-
vidually and for certain combinations of plants, locations, and times.
Combinations of data collected at the condenser outlet were pooled
and treated as independent populations. This treatment was necessitated
by the small sample size. Consequently, the intent of the partial corre-
lation analysis is not to draw definitive conclusions about the influences
of independent variables on chloroform yield. Rather the findings should
be indicative of which relationships appear to be promising for future
research efforts. Confidence levels of the pooled data were distorted by
the treatment as noncorrelated and, therefore, are not given in the results.
Once the significant relationships had been identified, simple linear
regressions and bivariate scatter diagram plots were run to establish the
most basic cause-effect relationships. For the reasons mentioned pre-
viously, and because the relations are actually much more complex than the
simple regressions allow, too much importance should not be placed on this
portion of the study.
The following section discusses the results of the research, begin-
ning with a description of the data base and the distributional character-
istics at each location, plant, and time. This is followed by the analysis
of within plant locational differences in chloroform concentrations and
the identification of the important related factors. Finally, the scatter-
gram plots and simple regressions are presented.
47
-------
Following are the results obtained from the statistical analysis of
the cooling water samples. The results from the Allen Plant are discussed
first, followed by those from Kingston Plant, and finally those from
Shawnee.
The semivolatile halogenated organic compounds were below detection
limits on all dates for all plants with three exceptions. At Allen Steam
Plant on September 25 and November 27, 1979, 2-chlorophenol was detected.
At Kingston Steam Plant on September 11, 1979, 2-chloronapthalene and
1,2-Dichlorobenzene were detected. These data are presented in Appendix A.
Because similar concentrations at the intake, condenser inlet, and
condenser outler were observed, no further analysis of the semivolatile
halogenated organic compounds is offered or felt necessary.
Locational Trends in Chloroform Concentrations
Trends in the chloroform measurements were tested for significance
levels using the nonparametric umbrella curve and multiple comparison test28'29
as described previously. This section of the report discusses these results.
Overall Trend in Data
The test that the data follow an umbrella shaped curve produced the
following results:
(1) Rank the observations for each day from smallest to largest.
Ranks are given in parenthesis.
Chloroform
LOCATION (L)
Int 00 Inlet 12 Outlet 12 Outlet 24 Outlet 35
1
2
3
4
5
6
7
8
9
2.90(1)
-50(1)
.50(1.5)
.50(5)
.05(1)
.08(1)
.08(1)
.10(1)
.08(1)
7.
8.
9.
t
3.
10.
4.
2.
5.
80(4)
00(4)
90(3)
40(3.5)
10(3)
00(4.5)
80(3)
50(3)
20(3)
4
8
11
5
9
5
2
5
.90(3)
.30(5)
.00(4.
.40(3.
.00(4)
.00(3)
.30(5)
.70(4.
.80(5)
5)
5)
5)
10
7
11
7
10
5
2
5
.00(5)
.80(3)
.00(4.
.30(1.
.20(5)
.00(4.
.20(4)
.70(4.
.50(4)
5)
5)
5)
5)
4.40(2)
.60(2)
.50(1.
.30(1.
.20(2)
.20(2)
.30(2)
.20(2)
.20(2)
5)
5)
(2) Sum the ranks assigned to each location
R! = 13.5 R2 = 31.0 R3 = 37.5 R4 = 36.0 R5 = 17
Location 3 has the largest sum of ranks.
48
-------
(3) Count the number of pairs of observations increasing up to the
third location and also count the number of pairs decreasing
after the third location.
A3 =4+6+ 5. 5 +3+5+4+6+ 5. 5 +6= 45
(4) Standardize AS to get
= 3-80*
(5) Compare A£ to table of distribution of A3
Therefore the initial Ho hypothesis of no trend is rejected in favor
of the alternative at the a«0.01 significance level.
Pairwise Comparisons
The multiple comparisons test results are given below:
Approximate Procedure (large N) Procedure (Exact)
Locations R.-
J
12 17
13 24
14 22
15 3
23 6
24 5
25 14
34 1
35 20
45 19
U - .U3
•R Critical Value
5 18.30
0 "*
5 "*
5
5
0
0
5
5 "*
0 "*
u — . ui
Critical Value
21.83
"*
tt-j'c
It
II
II
II
II
II
It
u - . uo/
19
"•/V
"*
II
II
II
II
II
"iV
ti,V
u - .uu
22
!!•&
""/V
II
II
It
II
It
II
II
Declare: L% ? L3 at a = .01 level
L! 7* L4 at a = .01 level
L5 ± L3 at a = .05 level
L5 / L4 at a = .05 level
Locations (in increasing
order)
152 43
^Indicates a significant difference at the a-level given at the top of
the corresponding column.
Increases in chloroform were most significant between the intake and
the outlet during chlorination. There was a significant difference at the
99 percent confidence level. At the 95 percent confidence level the dif-
ferences between the outlet during and after chlorination are significant.
If a 90 percent significance level is acceptable, the differences between
the intake and inlet are significant.
49
-------
FACTORS RELATED TO CHLOROFORM PRODUCTION
This section of the report is an analysis of the relationships between
chloroform concentration and a selected subset of precursors. The results
are presented at two levels. The first of the relationships tested was a
simple bivariate correlation between each of the variables. The correla-
tion coefficients were then tested for significance. The associated signi-
ficance levels are for the hypothesis of no correlation among the variables.
The second level was a partial correlation of each precursor against
chloroform, controlling for the effects of one other precursor and pair-
wise correlations controlling for two other precursors. Due to data
limitations this process could not be carried to its logical conclusion
of controlling for as many effects as possible, particularly when the data
from a single sample location was used.
Allen Steam Plant
The data base for the analysis at Allen is the most extensive and
hence the results for this plant are the most important. Tables 19
through 23 are matrices showing the simple (zero order) partial correlation
coefficients, and the number of degrees of freedom for the intake, inlet,
outlet at time 1, outlet at time 2, and outlet at time 3, respectively.
At the intake (Table 19) most of the relationships are not particu-
larly significant. None of the environmental precursors—pH, bromide,
nitrogen species, or substrate—shows a significant relationship with
intake chloroform concentrations. Substrate concentration versus chloro-
form concentration has a very high coefficient of 0.948, but more than
the three degrees of freedom available would be needed to show whether
the relationship is significant.
Chlorine dosage and temperature (intake) were also not significantly
correlated with chloroform concentrations. With respect to chlorine dos-
age this is expected since chlorine dosage would be independent of the
background chloroform concentrations in any case. However, free and total
residual chlorine exhibited negative correlations. These relationships
must be spurious since chlorine is not even present in the cooling system
at the intake. Their mutual variation in concentration must be coincidental,
The lack of a relationship with ambient temperature (r=0.0572,
D.F. = 3), suggests only that ambient seasonal temperatures vary randomly
or nonlinearly with background chloroform concentrations, or that, by
chance, a truly linear relationship was not observed in this particular
round of sampling.
At the inlet and outlet, time 1 and 2, some interesting relationships
appear. In particular the outlet chloroform versus chlorine dosage rela-
tionship becomes important and so does the correlation between chloroform
and nitrogen species. Both the positive relationship with chlorine dose
and the negative relationship with nitrogen species are consistent with
the currently accepted trihalomethane formation mechanism.
50
-------
TABLE 19. SIMPLE CORRELATIONS, ALLEN, INTAKE
CHLOR01
CLDOSAGE
FRCIN
TRCIN
pH
BRS
NSPECIE
SUBSTRAT
CHLOR01
1.0000
( ^0)
-.1560
( 6)
P= .356
-.5588
( 6)
P=
_
(
P=
_
(
P=
_
(
P=
(
P=
(
P=
.075
.6370
6)
.045
.1185
6)
.390
.2506
3)
.500
.0343
7)
.465
.9484
3)
.500
--rARili
CLDOSAGE
1.0000
( _ 0)
.6682
( 6)
P=
( '
P=
( "
P=
( '
P=
( '
P=
.
( '
P=
.035
2330
6)
.289
6066
5)
.074
1156
3)
.500
0377
6)
.465
8946
3)
.500
i -Li L. U tV K £
FRCIN
1.0000
( t o)
p=*
( '
P=
( '
P=
( '
P=
*
( '
P=
_
( '
P=
****
5638
6)
.073
1587
5)
.367
2230
3)
.500
2962
6)
.238
2549
3)
.500
i ii A i i u a
TRCIN
1.
(
P="
_
( '
P=
_
( "
P=
( '
P=
( "
P=
0000
,,0)
•****
3547
5)
.217
7103
3)
.500
3606
6)
.190
6437
3)
.500
L U £ r £ J. L
pH
1
(
P-
(
P=
_
(
P=
_
(
P=
.0000
0)
JLJLJL^JL
.2089
2)
.500
.1025
6)
.405
.8804
2)
.500
.J-UJN-IO---------
BRS NSPECIE
1.
(
P=
_
(
P=
_
(
P=
0000
0)
*****
.6772 1.0000
3) ( 0)
.500 p=*****
.4128 .6701
3) ( 3)
.500 P= .500
SUBSTRAT
1.0000
( o)
p=*****
-------
TABLE 20. SIMPLE CORRELATIONS, ALLEN, INLET
Oi
to
CHLOR01
CLDOSAGE
FRCIN
TRCIN
pH
BRS
NSPECIE
SUBSTRAT
CHLOR01
1.0000
( 0)
p—~n~'~!~n'-k
.3940
( 6)
P= .167
.5280
( 6)
P= .089
.0089
( 6)
P= .492
-.0976
( 6)
P= .409
-.0086
( 3)
P= .500
-.4769
( 7)
P= .097
.0991
( 3)
P= .500
- - r a K i i t
CLDOSAGE
1.0000
( 0)
P=*****
.6682
( 6)
P= .035
.2330
( 6)
P= .289
.6066
( 5)
P= .074
.1156
( 3)
P= .500
.0377
( , 6)
P= .465
-.8946
( 3)
P= .500
\ li b U K A i
FRCIN
1.
(
p=*
( '
P=
(
P=
( '
P=
_
( '
P=
_
( '
P=
0000
tiO)
"!w?XW
5638
6)
.073
1587
5)
.367
2230
3)
.500
2962
6)
.238
2549
3)
.500
\ Li A 1 J. U J.H
TRCIN
1.0000
( 0)
P=*****
-.3547
( 5)
P= .217
-.7103
( 3)
P= .500
.3606
( 6)
P= .190
.6437
( 3)
P= .500
L, u & r r ± i
PH
1.0000
( o)
p=w/wn«?
.2089
( 2)
P= .500
-.1025
( 6)
P= .405
-.8804
( 2)
P= .500
.. J. £i « 1 O - •
BRS
1.0000
( tt|0)
P=***"*
-.6772
( 3)
P= .500
-.4128
( 3)
P= .500
NSPECIE SUBSTRAT
1.0000
( iitO)
p_*****
.6701 1.0000
(3) (0)
P= .500 p=*****
-------
TABLE 21. SIMPLE CORRELATIONS, ALLEN, OUTLET, TIME 1
Ul
CHLOR01
CLDOSAGE
FRCIN
TRCIN
pH
BRS
NSPECIE
SUBSTRAT
CHLOR01
1.0000
( iitO)
P=/w!"/~r/r
.7038
( 6)
P= .026
.8575
( 6)
P= .003
.2886
( 6)
P= .244
.0922
( 6)
P= .414
.0795
( 3)
P= .500
-.4928
( 7)
P= .089
-.1590
( 3)
P= .500
- - r A K i i t
CLDOSAGE
1.0000
( _J>)
.6682
( 6)
P= .035
.2330
( 6)
P= .289
.6066
( 5)
P= .074
.1156
( 3)
P= .500
.0377
( 6)
P= .465
-.8946
( 3)
P= .500
\ L L U K K J
FRCIN
1.0000
( 0)
P=*****
.5638
( 6)
P= .073
.1587
( 5)
P= .367
.2230
( 3)
P= .500
-.2962
( 6)
P= .238
-.2549
( 3)
P= .500
1 i, A i 1 U JN
TRCIN
1.0000
( 0)
P=*****
-.3547
( 5)
P= .217
-.7103
( 3)
P= .500
.3606
( 6)
P= .190
.6437
( 3)
P= .500
L U Ji
P
1.
(
p=*
( '
P=
_
( "
P=
_
( '
P=
t! £ I (.
H
0000
_0)
IwwwC
2089
2)
.500
1025
6)
.405
8804
2)
.500
J 1 JB, JN T b - -
BRS
1.0000
( 0)
PS*****
-.6772
( 3)
P= .500
-.4128
( 3)
P= .500
NSPECIE SUBSTRAT
1.0000
( 0)
P=*****
.6701 1.0000
(3) (0)
p- .500 p=*****
-------
TABLE 22. SIMPLE CORRELATIONS, ALLEN, OUTLET, TIME 2
CHLOR01
CLDOSAGE
FRCIN
TRCIN
PH
BRS
NSPECIE
SUBSTRAT
CHLOR01
1.0000
( _J»
.5767
( 6)
P= .067
.3854
( 6)
P= .173
-.2466
( 6)
P= .278
.2041
( 6)
P= .314
.0707
( 3)
P= .500
-.5450
( 7)
P= .865
-.4679
( 3)
P= .500
• - f A K J. i t
CLDOSAGE
1.0000
( 0)
•rj^^*.JjJ-^-i.ij
h*.^A A A A A
.6682
( 6)
P= .035
.2330
( 6)
P= .289
.6066
( 5)
P= .074
.1156
( 3)
P= .500
.0377
( 6)
P= .465
-.8946
( 3)
P= .500
\ L L U K K 1
FRCIN
1.0000
( _ J3)
J-*^ A A A A A
.5638
( 6)
P= .073
.1587
( 5)
P= .367
.2230
( 3)
P= .500
-.2962
( 6)
P= .238
-.2549
( 3)
P= .500
1 li H 1 1 U IN
TRCIN
1.
( t
P— "
-
(
P=
_
( "
P=
( "
P=
( '
P=
0000
itO)
" «"'>
3547
5)
.217
7103
3)
.500
3606
6)
.190
6437
3)
.500
L u Ji r r 11
pH
1.0000
( tifO)
p_*****
.2089
( 2)
P= .500
-.1025
( 6)
P= .405
-.8804
( 2)
P= .500
^IJllNID---------
BRS NSPECIE
1.0000
( t o)
P~^C^? 4\*t\*t\
-.6772 1.0000
(3) (0)
p= .500 p=/v/'wwwV
-.4128 .6701
(3) (3)
P= .500 P= .500
SUBSTRAT
1.0000
( 0)
p=*****
-------
TABLE 23. SIMPLE CORRELATIONS, ALLEN, OUTLET, TIME 3
Ui
Ui
CHLOR01
CLDOSAGE
FRCIN
TRCIN
PH
BRS
NSPECIE
SUBSTRAT
CHLOR01
1.0000
( _o)
.2177
( 6)
P= .302
-.6123
( 6)
P= .053
-.6722
( 6)
P= .034
-.1389
( 6)
P= .371
.9301
( 3)
P= .500
-.0524
( 7)
P= .447
-.0756
( 3)
P= .500
- - r A K i i i
CLDOSAGE
1.0000
( _o)
P^wwC/CX1
( '
P=
( '
P=
( '
P=
( '
P=
( '
P=
( '
P=
6682
6)
.035
2330
6)
.289
6066
5)
.074
1156
3)
.500
0377
6)
.465
8946
3)
.500
\ L L U K K J
FRCIN
1.0000
( (tj)
.5638
( 6)
P= .073
.1587
( 5)
P= .367
.2230
( 3)
P= .500
-.2962
( 6)
P= .238
-.2549
( 3)
P= .500
1 L A 1 1 U N
TRCIN
1.
( j
( '
P=
( '
P=
( "
P=
( '
P=
0000
0)
•****
3547
5)
.217
7103
3)
.500
3606
6)
.190
6437
3)
.500
L ; o E t t i (
pH
1.0000
( _o)
.2089
( 2)
P= .500
-.1025
( 6)
P= .405
-.8804
( 2)
P= .500
J1ENTS
BRS NSPECIE SUBSTRAT
1.0000
( _ JO
-.6772 1.0000
(3) (0)
P= .500 p=*****
-.4128 .6701 1.0000
( • 3) (3) (0)
P= .500 P= .500 p=*****
-------
The lack of a simple linear relationship with some of the other
environmental variables, especially bromide and substrate, is not surpris-
ing. In fact, small sample size and negative correlation with total resi-
dual chlorine, nitrogen species, and substrate may obscure the actual
relationships for bromide. Substrate is correlated with chlorine dosage,
pH, and nitrogen species and controlling for these variables is necessary
for any true relationship with chloroform to be revealed. With only sin-
gle sample location data there were insufficient degrees of freedom to
perform the partial correlations.
To circumvent this problem, the results of the sample location tests
described previously were employed to pool the data in two ways:
combination of outlet, times 1 and 2
combination of inlet and outlet, times 1 and 2.
First, the simple correlations were run and examined to see if the basic
relationships observed with the single location data sets were maintained.
Table 24 shows the matrix for the outlet samples at times 1 and 2 combined.
As seen, the relationships with chlorine dosage, residuals, and nitrogen
species are maintained. The correlation problem still exists between
independent variables.
Partial correlations, controlling sequentially for other precursors,
are shown in Table 25. The effect of this procedure is to remove a com-
mon influence from the relationship between two variables.
When bromide, substrate, and nitrogen species were individually con-
trolled for, the relationship between chlorine dosage and chloroform is
strengthened. When simultaneous pairwise control is exerted, the residual
relationship is almost linear.
Control variables had no influence on correlations between free
residual chlorine and chloroform concentration. Total residual chlorine
versus chloroform was significantly affected by only one set of control
variables--pH and substrate simultaneously.
Partial correlations with pH versus chloroform were significant in
only one case. When both nitrogen species and chlorine dosage were con-
trolled for, pH was negatively correlated. This would tend to refute the
hypothesis that chloroform production is favored at high pH. There is a
direct effect of pH on chloroform production, but it is masked by the
variation of chlorine or nitrogen species in the systems.
The test hypothesis concerning a relationship between bromide ion
concentration and chloroform production was that they would be antagonis-
tic. The results of the partial correlations, while generally producing
negative coefficients, were not very significant. The exception was the
case where nitrogen species and chlorine dosage were controlled; the
relation was important in this case. On the other hand, control of chlorine
dosage and substrate produced a positive coefficient. It is not clear why
this result was obtained since the simple correlations with both substrate
and nitrogen versus bromide were negative.
-------
TABLE 24. SIMPLE CORRELATIONS, ALLEN, OUTLET, TIMES, 1 AND 2 COMBINED
Ui
CHLOR01
CLDOSAGE
FRCIN
TRCIN
PH
BRS
NSPECIE
SUBSTRAT
CHLOR01
1 . 0000
( 0)
.6283
( 14)
.6048
( 14)
.0130
( 14)
.1498
( 14)
.0739
( 8)
-.5155
( 16)
-.3233
( 8)
- r A K i i i
CLDOSAGE
1.0000
( 0)
.6682
( 14)
.2330
( 14)
.6066
( 12)
.1156
( 8)
.0377
( 14)
-.8946
( 8)
\ L LUKKiiLA
FRCIN
1
(
(
(
(
(
(
.0000
0)
.5638
14)
.1587
12)
.2230
8)
.2962
14)
.2549
8)
(
(
(
(
(
. T 1 U JN
TRCIN
1.0000
0)
__J>.-JLJLJL.A-
-.3547
12)
-.7103
8)
.3606
14)
.6437
8)
L u E a a i (
pH
1.0000
( 0)
.2089
( 6)
-.1025
( 14)
-.8804
( 6)
J 1 £ N T S - -
BRS
1.0000
( 0)
-.6772
( 8)
-.4128
( 8)
NSPECIE SUBSTRA
1.0000
( 0)
.6701 1.0000
(8) ( 0)
-------
TABLE 25. PARTIAL CORRELATION MATRIX - ALLEN, OUTLET, TIMES 1 AND 2
Chloroform Versus
Simple
Controlling For
(a)
Ul
oo
Chlorine Dosage 0.628
Free Residual Chlorine 0.605
Total Residual Chlorine 0.013
pH 0.149
Bromide Ion 0.074
Nitrogen Species -0.516
Substrate -0.323
(b)
0.684 0.626 0.756 0.802
5 1,2 1,3 1,4
0.685 0.876
0.599 0.546 0.559
1,5 2,3 2,4 2,5 3,4 3,5 4,5
0.952 0.973 -
0.630 0.588 - 0.557
0.595 0.605 0.552 0.571
0.072 0.093 0.249 0.305 - 0.142 0.621 - -0.072 0.340 - 0.281 -
0.138 0.114 -0.300 -0.374 - 0.223 -0.340 -0.380 - -0.680
0.044 - -0.437 -0.069 0.002 - -0.469 -0.198 0.073 - - - -0.441 -0.906 0.922
-0.509 -0.634 - -0.426 -0.694 -0.649 - - -0.822 - -0.581 -0.953 -
-0.408 -0.322 -0.0348 - 0.687 0.4448 0.075 - - - - 0.959 -
(a) 1 = ph
2 = Bromide
3 = Nitrogen Species
4 = Substrate
5 = Chlorine Dosage
(b) 0.0628 - r.. (coefficient)
-------
Control of other precursors, particularly bromide and chlorine dose,
strengthened the relationship between chloroform and nitrogen species.
The original hypothesis of a positive trend between substrate and chloro-
form concentration was not supported by the simple correlation or any of
the partial correlations except when controlling for chlorine dosage.
Since chlorine dosage and substrate were highly correlated in the simple
correlation, the true relationship between substrate and chloroform concen-
tration was obscured. Removal of the effects of chlorine dosage results
in a significant positive trend between chloroform and substrate.
Partial correlations run for other sets of pooled halogenated organic
data produced trends in a similar direction but weaker in terms of signifi-
cance. This was expected because the homogeneity of the underlying sample
distributions was not as great as the outlet, time I and time 2 data.
Only temperature showed some interesting trends. When the data for outlet
samples at all plants were combined and the effects of other precursors
removed, the relationship was significant. This suggests that the tempera-
ture affects the reaction rates and the types of species present in a
complex way.
Kingston Steam Plant
Only the simple correlations for the Kingston Plant, outlet, time 1,
time 2, and time 3 were performed. Other locations and correlation levels
were not attempted due to the small data set. Interpretation was not
generally attempted due to the small data set, but the relationships for
chlorine dose versus chloroform did not appear significant.
Shawnee Steam Plant
Only the simple correlations for the Shawnee Plant, outlet, time 1,
time 2, and time 3 were performed. Other locations and correlation levels
were not run due to the lack of data. The simple correlations for pH,
bromide, nitrogen species, and substrate had too few degrees of freedom for
interpretation. Chlorine dosage and residual chlorine exhibited the same
trends as were observed at Allen.
SCATTERGRAMS AMD LINEAR REGRESSIONS
For the Allen Plant outlet data (Figures 5 to 7) bivariate plots of
chloroform versus chlorine dosage, free residual chlorine (inlet), and
nitrogen species were run. These three precursors were selected because
they gave the best linear fit for the correlation analysis.
Scattergrams were also plotted of the logarithm of chloroform versus
the logarithm of substrate concentration (Figure 8). This transformation
did not improve the relationship significantly over that of a linear fit.
The second log-log plot of chloroform versus nitrogen species did improve
the relationship slightly (r, = -0.576, P=0.006 versus linear = -0.516;
P=0.014) (Figure 9). 8
59
-------
SCATf ERGRAMS, PLANT 1,L OCAS,TIME1, 2
FIGURE 5. SCATTERGRAM OF CHLOROFORM VFJISUS CHLORINE DOSAGE
09/05^80 16.07.29.
PAGE
Fi(-E OfJGPivES (CREATION DATE = 09/02/80 J
SUBFILE ORSJAT3
SCATFERGRAM
tDOWNI CHLOR01 CHLOROFORM
1.44300
11.0000
9. 930 0
8.6600
7.7900
6.7200
5.6500
<». 5800
3.5100
1.3700
.3000
-------
iCArrERG*AMS,PLANTl,LOCA3,TIMEl,2
FIGURE 6. SCATTERGRAM OF CHLOROFORM VERSUS FREE CHLORINE RESIDUAL »
09/05/80 16.07.29.
PAGE
sS&FiLE^olIo-ATP"110" UAI£ ' 09/02/8a '
SCATfEfcGRAH OF " (DOWN) "CHLOROl " CHLOROFORM
(AC*OSS) FfcCIN
.0970 .1110 .1250 .1390 .1530 .1670
11.0000 «•
I
I . _._ ... .
9.9300 »»
I
I
- &.86fH! * - - - '
I
. - - j. ----- . - _. .---_--
7.7000 +
I »
3.7200 «•
I
I
5.6530 » *
I »
I »
I »
1» *
^.5800 *
I
I
3.5100 »
I
I 2
Z.<*400 <•
I
i.sroa *
i
.340* i
.0900 .1040 .1180 .1320 . 1V6Q .1600 .171.0
STATISTICS..
CO?K£UriON (ftl- .60V79 S SQUASED - .36577
SIO ER? OF EST - 2.24307 INTERCEPT - VAt-tJES - 0 HISSING VALUES - 22
1810 .-1950 .2090 .2233
2*
I
I
...... -. -I-.
* *
I
: !
i
I
»
i
i
•»
i
*
i
i
*
i
{
«
i
4-
I
I
»
.1880 .2020 .2160 .2300
SIGNIFICANCE R - .00653
STD ERROR OF A - 2.20796
STO ERROR OF 6 - 12.74765
~i I/O 000
9.9300
8.8600
7.7900
6. 7 20 0
5.6500
4.5800
3.5100
2.4400
1.3700
.3000
-------
SCAnERGRAMS»PLANTl,LOCA3,TlMEli2
FIGURE 7. SCATTERGRAM OF CHLOROFORM VERSUS NITROGEN SPECIES
09/05/80 16.07.89.
PAGE
FILE OrtGPRES (-NATION DATE = 09/02/90 >
SUBFILE ORGOAT3
SCATTERGRAM OF IQOWN) CHLOR01 CHLOROFORM
(ACROSS) NSPtCIE
239.295 335.485 381.675 427.865 474.055 520
11.0000 +
I- -
I
9.9JOO + * *
I
I
8.8600 «• *
I
I
^
7.79QO «• *
7
i *
b.7200 t
$
I
5.6500 * I
r
4.5800 *
I
i
I
I
S.5100 *
I
I
I
I
1.3700 *
T
I
.3QflO * +
266.200 312.390 356.560 i»0<*.770 l»50.960 ^97.150
STATISTICS..
CORRELATION - -.51550 s SQUARED
iT3 ERR OF EST - 2.9<.738 |N«iI|CfSI (A» "
S-KN£FI»ANGE A — - .80M3 - SLOPE <34
SliNIFICrtNCE B - . 011*28
-ptOTFtO VftLUES - 18 EXCLUDED VALUES - 0 MISSING VALUES -
.245 566.W5 612,625 658.815 705.005
2 *
I
4
I
I
I
4
I
I
I
4
I
I
I
*
I
$
I
4
I
I
I
*
I
I
21
I
I
4
I
I
2 *
5<»3.3<»0 589.530 635.720 681.910 728.100
.265T<» SIGNIFICANCE R - .Sl<»28
10.68817 STD ERROR OF A - 1.979ii9
-.00970 STD ERROR OF B - .00*03
20
11.0000
9.9300
8.8600
7.7900
6.7200
5.6500
4.5800
3.5100
2. <»
-------
FIGURE 8. SCATTERGRAM OF LOG CHLOROFORM VERSUS LOG SUBSTRATE
SCATTERGRAMS,PLANT1,LOCA3,TIME1,2 C9/06/80 16.17.05. PASE
OJ
SCATTERGRAM OF' (DOWN) LOGCHLOR NATURAL LOG OF CHLOROFORM
tACROSS) LOGSUBST NATURAL LOG OF SUBSTRATES
-.28 -.11, .01 .15 .38
Z.M + " .--...-
I
I
2* * i*
i . . . .
1.S8 *
1.32 I
I
.95 +
i
.»• i
,J
i
-.12 »
I
— » * 8 + -------
I
I
-.91, +
-1.21 +
-.36 -.21 -.07 .08 .23 .37
STATISTICS..
coRREHTluN
SIGNIFICANCE 8 - .19728
-PL&TTEO VALUES - 19 EXCLUDED VALUES - 6 HISSING VALJES -
.<»<• .59 .73 .88 1.C3
+ g.^C
9 - j-- . - . ,
I
+- 2.6*
I
I
: I
i
+ 1.32
Z+ .96
1 .60
I
+ .24
I
I
i
i
i
i
i
,+ + . . . . . . . .* -i-2«i
.52 .66 .3i .95 1.1(2
.09188" STG~KTFIC~A~f!CE~ R~- .19728 —
1.83932 STD ERROR OF A - .22076
-.2*085 STD ERROR OF fl - .26682
28
-------
FIGURE 9. SCATTERGRAM OF LOG CHLOROFORM VERSUS LOG NITROGEN SPECIES
SCATTERGRAMS,PLANTl,LOCA3,TIMElt2
S9/05/80
16.17.C5.
PAGE
PILE ORGPRtS (CRiiATION DATE = 09/02/80 )
SUBFILE ORGDATS
SCATTERGRAM OF" (OOHN) LOGCHLOR NATURAL LOG OF CHLOROFORM
(ACROSS) LOGNSPEC NATURAL LOG OF NSPECIE
5.63 5.74 5.84 5.94 6.C4
I »
I »
2.J4 j
T
1 - "
1.68 *
T? *
I
i
1.32 «•
I
.96 *
I
.66 *
»
*
.24 j
I
I
I
-.12 *
I
I
-.48 +
I1
I
-.»4 «•
I
j
-1.20 *
5^58 * 5.68 5.79 5.89 5.99 6.89
STATISTICS..
CORRELATION CR1'- -Y5T638 R SQUARED
STO E»R OF EST - .86967 INTERCEPT
-------
Least-squares linear regressions of chloroform versus a precursor
variable were run in conjunction with the scattergrams, .
The regression fit of chloroform concentration versus chlorine dose
resulted in the following relationship:
Conception W> = 4'36 tchl°rine d°Sa*e (^/1)] + ^ '
The standard error of prediction for the regression was 2.20 |Jg/l with
39.5 percent of the variance in the chloroform concentrations explained by
chlorine dosage. While this is a substantial percentage, it indicates that
other variables singly and in conjunction are responsible for the majority
of variance or that there is considerable random variability. Since the
partial correlations showed that nitrogen species, bromide, and substrate
were also involved, the results of the simple regression analysis are not
surprising.
The regression equation also implies that the background chloroform
concentration (that is, in the absence of chlorination) would be 1.58 (Jg/1-
This is higher than the actual value of 0.53 pg/1 and may stem from the
fact that the significance level of the intercept is relatively low (P =
0.20) and from the large standard error (35.2 percent relative to the mean
chloroform concentration of 6.23 (Jg/1). It may also indicate that a linear
model does not extrapolate to background conditions.
The results also suggest that the change in chloroform concentration
at the outlet is 0.00436 times the change in chlorine dosage when both are
in equivalent weight units. On a molar basis the relationship suggests
that the change in chloroform concentrations (|JM) is 0.0118 times the
chlorine dosage in (Jmoles per liter as HOC1.
For free residual chlorine the regression equation was:
Concentration ^S/1) = 36'22 tFree Residual Chlorine (mg/1)] + 0.895
The standard error of prediction for the regression was 2.25 Mg/1 with
36.6 percent of the variance in chloroform concentration explained. The
other variables appear to still require inclusion in a predictive equation
since a majority of the variance is unexplained, or else considerable ran-
dom variability is present.
The predicted background chloroform concentration of 0.895 |Jg/l is
closer to the actual value; however, the significance level of the value
of the intercept is low (P = 0.35) and the relative standard error is
still high (36.1 percent).
When the statistical outlier point was rejected as being greater than
two standard errors from the least square line, the following regression
was obtained:
65
-------
Concentration (|Jg/1) = 55'79 [Free Residual Chlorine (mg/1)] - 2.87
Again, the estimated background concentration is incorrect, however,
the fit to the straight line is very good (r = 0.869). This relationship
also explains the majority of variance in the chloroform concentrations
(75.6 percent) and implies that free residual chlorine at the inlet may
be a better predictor variable than chlorine dose. In addition, the free
residual chlorine exhibited fewer confounding effects in the partial cor-
relations, indicating that the prediction is less influenced by other
variables.
The regressions of nitrogen species versus chloroform showed more
scatter than the other regressions (r = -.516) and nitrogen species did
not explain as large a portion of the variance as the chlorine precursors.
The resulting regression fit was:
Chloroform ( } =
Concentration ^°
Nitrogen
Species (pg/1)
Concentration
+ 10.69
The standard error of prediction for the regression was 2.95 |Jg/l with
26.6 percent of the variance explained.
Regression on the log-log plots produced the relationship:
Log Chloroform _ .. „
Concentration ' °e
Nitrogen
Species
Concentration
(P8/D
+ 10.91
This equation predicted with a standard error of 0.870 log concentra-
tion units and explained 33.2 percent of the variance in the chloroform
concentrations.
66
-------
REFERENCES
1. Stevens, A. A., C. J. Slocum, D. R. Seeger, G. G. Robeck. 1975.
Chlorination of Organics in Drinking Water. Proceedings of the Con-
ference on the Environmental Impact of Water Chlorination. July 1976:
85-114.
2. Federal Register, Volumn 45, No. 231, Environmental Protection Agency
(November 28, 1980), p. 79318.
3. Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants. USEPA-1978.
4. Vallentyne, J. R. The Molecular Nature of Organic Matter in Lakes
and Oceans, With Lesser Reference to Sewage and Terrestrial Soils.
J. Fish, Res. Board Can. 14, 33-82 (1957).
5. Morris, J. C., and G. McKay. March 1975. Formation of Halogenated
Organics by Chlorination of Water Supplies. USEPA Report No. EPA-600/
1-75-002.
6. Midgley, D. October 1979. Review of the Reactions of Organic Com-
pounds in Chlorinated Cooling Water. Central Electricity Generating
Board. Job No. VF155.
7. de la Mare, P.B.D., A. D. Ketley, and C. A. Vernon. The Kinetics and
Mechanisms of Aromatic Halogen Substitution. I. Acid-Catalyzed
Chlorination by Aqueous Solutions of Hypochlorous Acid. J. Chem.
Soc. 1290-1297 (1954).
8. Sykes, P. A Guidebook to Mechanism in Organic Chemistry. John Wiley
and Sons, New York (1961).
9. Kavanaugh, M. C., A. R. Trussell, John Cramer, and R. R. Trussel, "An
Empirical Kinetic Model of Trihalomethane Formation: Applications
to Meet the Proposed THM Standard," Journal American Water Works
Association, 578-582, (October, 1980).
10. Peters, C. J., R. J. Young, and R. Perry, "Factors Influencing the
Formation of Haloforms in the Chlorination of Humic Materials,"
Environmental Science and Technology, 14, 1391-1395, (November 1980).
11. Vigon, B. W., and T. G. Stanford. "Analysis of Volatile and Semi-
Volatile Halogenated Organic Compounds, Precursors, and Amino Acids
at Selected TVA Power Plants," Battelle-Columbus Division Report to
the Tennessee Valley Authority (June 1980), unpublished.
12. Am. Public Health Assoc., Standard Methods for the Examination of
Water and Wastewater, 14th Edition, (1975).
13. HNU Corporation, "Manual for Ammonia Electrode," unpublished.
14. HNU Corporation, "Manual for Bromide Electrode," unpublished.
67
-------
15. Schnitzer, M. and S. U. Khan. Humic Substances in the Environment,
Marcel Dekker, New York (1972).
16. Mantoura, R.F.C. and J. P. Riley. "The Analytical Concentration of
Humic Substances from Natural Waters," Anal. Chem. Acta. 76, 97-106
(1975).
17. Encyclopedia of Chemical Technology, edited by R. E. Kirk and D. F.
Othmer, 2nd Edition, Interscience Encyclopedia, New York (1947).
Volume 16, pp. 190-218.
18. Einhorn, A., J. Cobliner, and H. Pfeiffer. Ber., 37, 119 (1904).
19. Fatiadi, A. J. and W. F. Saeger. Org. Syn. 42, 66, 91 (1962).
20. Hubaux, A., and G. Vox. "Decision and Detection Limits for Linear
Calibration Curves," Anal. Chem., 42(8), 849-55 (1970).
21. "The Analysis of Trihalomethanes in Finished Waters by the Purge and
Trap Method," Method 501.1, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio.
22. "Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants," Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio, March 1977 (Revised
April 1977).
23. "Addendum to Sampling and Analysis Procedures for Screening of Indus-
trial Effluents for Priority Pollutants," Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio, April 1979.
24. "Trace Analysis of Organics in Water," GC Reporter, Supelco, Inc.
Newsletter, Vol. IV, No. 1, March 1979.
25. Vigon, B. W., and T. G. Stanford. "Analysis of Volatile and Semi-
Volatile Halogenated Organic Compounds, Precursors, and Amino Acids
at Selected TVA Power Plants," Battelle-Columbus Division Report to
the Tennessee Valley Authority (June 1980), unpublished.
26. Vigon, B. W., T. A. Bowen, M. L. Brown, M. Hunter, and W. J. Sheppard.
"Current Status of Alternative Biocides for Use in Electric Power
Generating Stations," Batelle-Columbus Division Report to the Tennessee
Valley Authority (July 1980).
27. Nie, N. H., C. H. Hull, J. G. Jenkins, K. Steinbrenner, and D. H.
Bent. SPSS: Statistical Package for the Social Sciences, 2nd
Edition, (New York:McGraw-Hill), (1975).
28. Mack, Gregory A. and Douglas A. Wolfe, "k-sample Rank Tests For
Umbrella Alternatives," 1980, to appear in Journal of the American
Statistical Association.
68
-------
29. Mack, Gregory A. "Distribution - Free Test for Umbrella Alternatives
in Randomized Block Designs," to be submitted for publication (1980).
30. Hollander, M. and D. Wolfe. "Nonparametric Statistical Methods,"
John Wiley and Sons, Inc.: N.Y. (1973), p. 151.
31. Ostle, B. Statistics in Research, (Ames: Iowa State University
Press), (1963).
69
-------
APPENDIX A
DATA FOR VOLATILE AND SEMIVOLATILE
HALOGENATED ORGANICS FOR ALL PLANTS
A-l
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (ng/1)
Performed by TVA Laboratory Branch
rv>
Allen 6/5/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
Allen 6/19/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
0
0
2
7
4
10
4
0
0
0
0
8
8
7
0
0
£3
S_i
o
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0
, — 1
u
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c js
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4J g
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1f
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (pg/l) (Continued)
Performed by TVA Laboratory Branch
> Allen 7/10/79
00 Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Allen 8/7/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
E
o
M-l
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0
1— 1
A
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<0.05
0.7
0.5
9.9
11.0
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0.5
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O>
N
a
01
f>
o
i-l
0
r— 1
O
<0.05
If
tt
If
ft
tl
tt
ft
<0.05
tt
tt
tt
tt
tl
11
11
utane
L r~)
o
o
rr|
U
•H
1
^^
rH
<0.05
ft
ft
ft
ft
tl
It
tt
<0.05
tt
tl
tt
ft
tl
tl
11
hloroethylene
u
•H
f~\
1
CSI
rH
1
W
a
CO
^
<0.05
it
tt
tt
"
tt
tt
it
<0.05
It
11
tt
tt
tt
tt
II
ropane
(•%!
O
l-l
o
rH
ft
O
• H
PI
m
rH
<0.05
tl
ft
ft
II
tl
tt
tf
<0.05
tf
It
tt
tl
tl
tl
II
chloroethane
CTJ
•M
OJ
1
r.
f\]
«\
rH
rH
<0.05
It
tt
It
It
tt
ft
tt
<0.05
n
"
tt
n
n
n
it
01
01 a
a o>
CO rH
O ft
i-l 4->
£LI OJ
0 O
0 0
i-H rH
ft ft
U O
•H -H
O O
1 1
01 rH
r-t fH
<0.05 <0.05
It M
11 It
II It
11 11
11 11
11 11
II 11
<0.05 <0.05
It 11
If 11
It tt
It tt
It It
ft tt
It It
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
> Allen 8/21/79
1
-p-
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Allen 9/25/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
1
i
0.
0.
0.
3.
5.
7.
0.
0.
<0.
0.
0.
10.
9.
10.
0.
0.
o
4H
0
I-l
0
-H
XI
U
1
1
05
1
0
2
2
3
05
1
08
0
0
0
2
1
0
0
B
0
1-1
PQ
<0.05
tf
tf
tf
tf
fl
11
II
<0.05
tt
II
It
ft
tt
It
tf
Sromochloromethane
HM
<0.05
II
It
ft
ft
tt
ft
11
<0.05
11
11
If
11
tf
It
tf
<0
<0
<0
0
0
1
<0
<0
<0
<0
<0
1
1
1
<0
<0
iromodichlorome thane
VM
.05
.05
.05
.7
.9
.0
.05
.05
.05
.05
.05
.1
.0
.8
.05
.05
<0
<0
<0
<0
<0
0
<0
<0
<0
<0
<0
0
0
0
<0
<0
Jibromochlorome thane
I-H
.05
.05
.05
.05
.05
.2
.05
.05
.05
.05
.05
.3
.2
.3
.05
.05
'richlorofluoromethane
lethyl Bromide
lethyl Chloride
C~i f-i i^-i
<0.05 <0.05 <0.05
n M ti
n n M
It It M
It tl II
It II II
II It II
II tt II
<0.05 <0.05 <0.05
n tt ii
n n n
n n n
n ti n
n tt ti
ti tt ti
n tt ti
tu uu
•O ti ti
•H 10 10
U XI XI
0 4J 4->
rH U tU
XI U 0 O
0 ti M S-l
to O 0
> SH « PH
XI O II
4-1 rH rH CM
D Jd -
SO rH rH
<0.05 <0.05 <0.05 <0.05
" " " <0.05
II II II o 0g
n tt ii 03
" " " <0.05
" " " <0.05
n M M 0-1
ii if ii 02
<0.05 <0.05 <0.05 <0.05
" " " <0.05
" " " 0.08
" " " <0.05
" " " <0.05
" " " <0.05
" " " <0.05
0.06
larbon Tetrachloride
\-s
<0.05
II
11
II
M
II
II
fl
<0.05
"
"
"
it
it
tt
tt
L , 1 , 1-Trichloroethane
0.1
0.3
0.4
1.0
1.0
0.4
0.8
0.1
0.3
0.5
1.0
1.1
1.7
1.0
1.3
1.0
^hlorobenzene
L , 4-Dichlorobutane
<0.05 <0.05
II 11
It II
It II
tt II
It II
II tt
11 tt
<0.05 <0.05
It 11
II 11
II 11
II It
II 11
II M
II It
:rans-l,2-Dichloroethylene
<0.05
tt
n
tt
it
it
n
n
<0.05
II
II
II
11
11
It
11
L , 3-Dichloropropane 1
<0.05
n
n
n
n
M
M
II
<0.05
ft
ft
ft
tt
ft
If
tt
1,1,2, 2-Tetrachloroethane
1 , 2-Dichloropropane
<0.05 <0.05
tt tt
tt tt
n tt
n ti
n ti
11 M
It It
<0.05 <0.05
tt It
tt II
tt II
tl tt
It It
tl II
fl It
1 , 1-Dichloroethylene
<0.05
tt
tt
tt
it
tt
n
n
<0.05
11
11
11
tf
11
11
11
-------
Allen 11/27/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
1
VJ1
Allen 10/16/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Chloroform
<-j
0.06
*
0.08
4.8
5.3
5.2
0.3
0.4
iromoform
iromochlorome thane
iromodichlorome thane
M-l P4 W
<0.05 <0.05 <0.05
* * *
<0.05 <0.05 0.3
" " 1.1
1.3
" " 1.4
" " 0.9
" " <0.05
libromochlorome thane
M
0.2
*
0.5
1.0
0.9
1.0
0.8
0.6
01
g
M "C
4_) O> OJ Ol -i-
Cl T3 (3 S3 t
g -H a co c
O 0) tl J3 J3 i-
tl Ol T3 O 4J 4-1 .£
O T3 -H rH CU OJ (.
3-Htlj30) O O ci
rHBOOfi tltlt
4-1 O i— 1 CO O O 4-
O tl J3 01 J3 rH rH 0
ti cq u (3 4-1 JE3J3E-
O (U OJ U O
rH i— 1 i— 1 t— 1 O -H -H C
0 J3 J=! J3 0 1 1 rC
•H4-l4-14-lrH r-l CM i.
EHSS^O i— ti— IC_
<0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.
* * * * * * * *
<0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.
It tt It tt tt It II Q
It It 11 tt It II tt Q
ft It II It It II It Q
It It It It tl tl tl CN
)
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
ON
Allen 12/11/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
Kingston 6/26/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
0
<0
0
5
5
5
0
0
0
0
0
3
4
4
0
0
E s
O i->
m o
O 4H
n o
0 E
rH O
JS H
.06 <0.05
.05 "
.08 "
.2
.8
.5
.2
.1
.3 <0.05
.3
.3
.4
.8
.4
.2
.3
loromethane
chlorome thane
si -H
O T3
0 0
E S
0 0
CQ PQ
<0.05 <0.05
" <0.05
" <0.05
0.4
0.5
" 0.5
" <0.05
" <0.05
<0.05 <0.05
" <0.05
" <0.05
0.3
0.7
0.7
" <0.05
" <0.05
chlorome thane
o
E
0
S-l
,0
•H
Q
<0.05
II
ft
It
It
II
It
11
<0.05
ti
ti
ti
n
ti
n
ti
rofluorome thane
Bromide
o
rH rH
U J=!
•r-f 4->
^•l QJ
H IS
<0.05 <0.05
If II
tt tt
It tt
It II
If ff
If fl
If II
<0.05 <0.05
n it
ii n
n n
n n
n n
M tt
it n
CJ
-H
O
i— 1
T— t
J=i
4J
CU
<0.05
II
II
tt
It
ft
If
If
<0.05
it
n
n
n
"
"
n
CU
•o
-H
0
rH
CD
d
CD
rH
r«
4-1
CD
<0.05
11
tt
tt
ft
It
If
II
<0.05
n
n
n
n
n
n
n
cu
d
CO
4-1
O
0
rH
si
CJ
<0.05
fl
If
If
11
If
II
It
<0.05
II
tt
tl
II
II
II
tt
hloroethane
hloroethane
U U
•H -H
Q Q
i i
rH OJ
f. r.
i-H r-H
<0.05 0.2f
0.2t
0.2t
" 0.2f
0.2t
0.2t
0.2t
" 0.2f
<0.05 <0.05
tt ti
tt n
it n
n it
it it
tt it
tt M
Tetrachloride
d
o
^ r\
^4
CO
U
<0.05
<0.05
0.08
0.06
0.1
0.1
0.08
0.06
<0.05
tt
ft
II
ft
tt
U
tt
richloroethane
E— i
i
i— i
*•<
i — i
VS
rH
<0.05
<0.05
0.7
0.5
0.4
0.4
0.5
0.2
<0.05
ft
ff
tt
tl
ft
11
tt
enzene
hlorobutane
,n
O rH
<0.05 <0.05
11 11
II M
tl 11
tt II
II II
It tt
11 tt
<0.05 <0.05
11 11
11 It
11 If
II tt
11 ff
fl ff
II tf
, 2-Dichloroethylene
i— i
i
w
(3
nj
^_i
4J
<0.05
It
fl
ft
ft
If
H
1!
<0.05
tt
tt
tt
II
11
II
11
hloropropane
U
•H
f~~\
I
CO
n
i — 1
<0.05
ff
If
It
tt
It
tl
tt
<0.05
It
tt
tf
ft
If
tt
ff
-Tetrachlo roethane
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
Kingston 7/10/79
> Lab Blank
-q Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Loroform
>moform
i i w
JS SH
U PQ
>mo chlo r ome thane
w
r-l
PQ
Laboratory blank not
0
0
3
3
4
0
0
.04 <0.05
.2 "
.2
.0 "
.3 "
.4 "
.2
<0.05
It
tt
"
tt
II
tt
<0
<0
0
0
0
<0
<0
)modichlorome thane
) romo chlo r ome thane
^ ij-i
U -H
PQ (P
recorded
.05 <0.05
.05 "
.4 "
.6
.5
.05 "
.05 "
S
CO 0)
J* T3
4-> CU 0) tU -rt
tU T3 ti ti H
B -r) C8 18 O
O (U M J3 J3 rH
M 0) T3 O 4-> 4J JS
O T3 -H i— 1 0) * l-l CnA O
o JS JS jti 0 I I ^
jHCUQJtUJI] ~ «CO
EHSSSO rHrHCJ
on this date.
<0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
It tt It It 11 tt M II
tt It II If II II 11 II
tl II II If II II II II
tt tt It If It tt It tt
II tl tt tf II tt H tt
tt tt tt 11 II tt tt 11
<0
1
<0
<0
<0
<0
<0
L , 1-Trichloroethane
-
r~l
.05
.4t
.05
.05
.05
.05
.05
Lorobenzene
t-Dichlorobutane
J3
u
<0.05 <0.05
tt it
tt u
u it
ti it
if ti
M u
0)
ti D
tu d
rH CO
>> JS
ja j-i
•U (U OJ
01 tu o tu e
o ti u d >
rH O JS O X!
JS !H <-> >H 4->
U fK « Pi 0)
•H 0 h 0 O
Q H 4J H *-l
1 O tU O O
CM i-H H rH rH
rH U CM CJ O
1 -H ~ -H -H
to O CM O O
ti 1 ~ 1 1
(H - -
<0.05 <0.05 <0.05 <0.05 <0.05
11 It II II II
II 11 tt tt 11
tt 11 tt tt tl
tt tt tt II It
It 11 tt tt II
II tt II tt tt
Kingston 8/7/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
0.08 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
0.2
0.1
4.4
7.2
5.4
0.1
0.1
<0.05 <0.05
<0.05 <0.05
0.4 <0.05
1.0 0.9
1.0 0.09
<0.05 <0.05
<0.05 <0.05
0.2
0.2
0.2
0.5
0.5
0.6
0.8
0.2
<0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
tProbable contamination
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
1
oo
Kingston 8/21/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
t
<
t+
<
S
c
1—
J
c_
1.
5V
0.
2.
4.
3.
0.
0.
iromoform
8t <0.05
*
07 <0.05
1
3
6
1
1 "
Iromochlorome thane
CM
<0.05 <0
*
<0.05 <0
" 0
0
" 0
" <0
" <0
Iromodichloromethane
libromochlorome thane
'richlorofluorome thane
pq H t-i
.05 <0.05 <0.05
* * *
.05 <0.05 <0.05
.3
.7
.6 " "
.05 "
.05 "
OJ
ti
01
1— t
0) XI
01 a 4-1
•a to oi
01 01 0) -H Xi 01 O
T3 a a s-i 4-> d sj
•H 10 to O tU to O
OIS-I XIXlr-HO 4-li-H
OJ-OO 4-l4->X|S-l 3 XI
•a-Hr-H o> xl xl E-i s-i a; xl
0)01 OO E-iXlOi-i
l— 1 i— 1 i— 1 O -rt -H d 1 O -H 1
>»>*>iS-l O Q O »— i S-l PI CO
xlxlxlo i ixi ^oid
4J 4J 4-1 i— 1 i— 1 CM S-l f-H i— 1
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
Kingston 10/10/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Kingston 11/14/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
0.
0.
Chloroform
2
2
<0
*
6.
4.
5.
3
0
0
<0
*
<0.
0.
0.
0.
4.
4.
3.
0.
0.
05
06
2
2
4
0
6
2
08
<0
<0
<0
<0
0
0
0
<0
<0
Bromoform
.05
It
*
.05
"
tt
*
.05
.05
.05
.05
.2
.2
.2
.05
.05
Bromochlorome thane
<0.05 <0
" <0
.ft.
<0.05 0
0
0
*
<0.05 <0
<0.05 <0
" <0
" <0
0
0
0
" <0
" <0
cu
a
CU cu CO CU
a a -a -o
CO CO 4-1 CU CU 0) -H
xs -a a 4-1 x! x! E-i
•HOC CU CU CJ O
T3 £ r— It— 1 r— ( i— 1 O -H'H a
O O X! t>* E>} K*% S-l £3 £3 O
E SH U x! X! XI 0 I ixi
O XI -H 4-1 4-1 4-1 r— 1 i-H CN S-t
S-i -H S-l CU CU CU X! - -CO
P3 Q H S S S 0 I-H rH C_>
.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
nc n tt n n tt it tt tt 11
* * * # * * * * * *
.5 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
A n tt tt it tt it it n 11
0 11 11 11 11 tt 11 11 11 11
•sV * iV * * * * * * *
.05 <0.05 , X3
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (pg/1) (Continued)
Performed by TVA Laboratory Branch
Kingston 12/18/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Shawnee 6/12/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
B
O
tf^
0
0
i-H
•ti
0.1
0.1
0.08
3.8
4.8
4.5
0.1
0.1
0.4
*
0.9
*
10.0
10.0
0.6
0.4
rm
lorome thane
0 43
4H U
0 0
E B
0 0
M pq
<0.05 <0.05 <0
ii tt <0
it tt <0
it u Q
II tt Q
it n 0
ti ,i <0
ii ii <0
<0.05 <0.05 <0
* *
<0.05 <0.05 <0
* *
<0.05 <0.05 2
ii tt 2
ti tt <0
it M <0
chloromethane
•H
T3
0
B
0
(H
.05
.05
.05
.5
.6
.7
.05
.05
.05
A
.05
*
.2
.2
.05
.05
chloromethane
0
B
0
u
fl
•H
<0.05
<0.05
<0.05
0.08
0.08
0.08
<0.05
<0.05
<0.05
*
<0.05
*
0.4
0.4
<0.05
<0.05
rofluorome thane
0
i-H
43
CJ
•H
H
<0.05
It
tt
ft
11
It
tl
It
<0.05
*
<0.05
*
<0.05
"
u
ti
Ol
T3
-H
0) !H
(U T3 O
T3 -H i— 1
•H U 43
SOU
0 i-H
H 43 01
M 0 ti
Ol
i-H i-H rH
^» t>i ^>
43 43 43
•P 4-> 4->
Ol Ol Ol
«sr* ^rt ^-i
lij it-t i->
<0.05 <0.05 <0.05
" " <0.05
1.1
60.0
16.0
5.0
" " 30.0
" " 0.08
<0.05 <0.05 <0.05
* * *
<0.05 <0.05 <0.05
iV -?\ "sV
<0.05 <0.05 <0.05
it ii it
u n it
u it it
01
ti
CO
Ol
o
o
rH
43
<0.05
If
tl
tt
It
tl
tl
II
<0.05
*
<0.05
*
<0.05
it
"
it
hloroethane
hloroethane
u o
•H -H
1 1
rH CM
rH rH
<0.05 <0.05
tl tl
tt tt
tt 11
tt It
tt tl
tl M
tl If
<0.05 <0.05
/v «•
<0.05 4.0
* *
<0.05 2.7
3.5
3.9
3.7
Tetrachloride
richloroethane
EH
ti 1
O rH
S-l rH
CO
U rH
<0.05 0.3
0.07 0.3
0.1 0.1
0 . 05 0.3
0.1 0.2
0.06 0.2
0.06 0.1
<0.05 0.2
<0.05 <0.05
?v «•
<0.05 <0.05
* *
<0.05 <0.05
it ii
u M
M n
enzene
o
o
!H
O
rH
U
<0.05
It
tt
tl
It
II
II
11
<0.05
*
<0.05
*
<0.05
it
tt
"
hlorobutane
, 2-Dichloroethylene
O rH
•H 1
Q M
i ti
-d- co
n
<0.05 <0.05
tt tt
tt It
ft ft
11 11
11 It
tt 11
It II
<0.05 <0.05
«• /V
<0.05 <0.05
A A
<0.05 <0.05
ii n
n M
M n
hloropropane
-Tetrachloroethane
hloropropane
O CM O
•H - 'H
o CM pa
i - i
CO rH
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (|Jg/l) (Continued)
Performed by TVA Laboratory Branch
B
t-t
o
m
0
n
0
r— t
XI
CJ
Shawnee 6/26/79
|!_, Lab Blank
H Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Shawnee 7/24/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet-1
Outlet-2
Outlet-3
Intake
0.
*
0.
9.
9.
9.
0.
0.
0.
0.
0.
6.
18.
18.
0.
0.
3
3
5
6
7
5
3
1
1
2
0
0
0
2
2
Br omoform
Br omochloromethane
Bromodichloromethane
<0.05 <0.05 <0.05
* * *
<0.05 <0.05 <0.05
" " 1.1
1.2
n „ 1-4
" " <0.05
" " <0.05
<0.05 <0.05 <0.05
" " <0.05
" " <0.05
0.1
0.8
0.6
" " <0.05
" " <0.05
0)
d
0) co
d xl
to 4-1 01 01
XI 0) T3 d
4-1 E 'H CO
O) O 0) H XI
E ^ CU T3 0 4-1
C O T3 -r-t I — 1 CU
n d -T-I M xJ o) o
O r-< S O CJ d !-t
r— 1 "4H O i-H CO O
XI 0 t4 XI 01 XI r-<
CJ 1-1 PQ CJ d 4J XJ
O O 0) 0) O
E r— 1 t-H I— 1 r-l O 'H
0 X! >•>>>> M O
^4 0 XI XI XI 0 1
Xl 'H 4J 4-> 4-1 i—t i-l
•r-4 1-1 0) Ol 0) X!
Q H S S S CJ rH
<0.
*
<0.
0.
0.
0.
<0.
<0.
<0.
tt
tt
11
It
tt
tt
tt
05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
******
05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
O 11 It tl It It It
0 11 tl II tt It tl
r\ 11 ft II tt tl tl
05 " " " " " "
QC II tt II tt 11 II
05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
tt II II 11 ft ft
11 tl tt tt It tt
11 ft It It It It
tl tl It It tl 11
It II It 11 If tt
tt 11 11 11 ft II
H tl It If II M
CD
d 0)
> ^
qj jj -P
d !-i co O cO
cOOCU 03 O PM •— i O^
jCJrHO 4-J>-HO^O
4JXIM d .CJ H L» H
(DCJOCU^Uf^^Pn
O C0»— (CJO-HOi-l O
UH^JOJUQ^-MH
O-PCJNOI O
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES ((Jg/l) (Continued)
Performed by TVA Laboratory Branch
I
H
ro
Shawnee 8/14/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
Shawnee 10/2/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
o
14-1
o
VI
o
1— 1
o
0.05
0.1
0.2
5.0
5.0
5.0
0.2
0.08
0.2
0.3
0.2
13.6
12.0
8.0
0.6
0.5
•m
oromethane
W i— 1
O J3
*4H U
0 O
E e
0 O
Vl Vl
m 09
<0.05 <0.05
tl II
It II
tt Jt
11 II
It tt
II tl
II tt
<0.05 <0.05
" <0 . 05
" 0.4
0.3
11 0.4
0.6
0.3
0.4
hloromethane
u
•H
T3
O
o
Vl
PQ
<0.05
<0.05
<0.05
0.4
0.4
0.4
<0.05
<0.05
<0.05
<0.05
<0.05
1.8
1.7
1.2
<0.05
<0.05
hloromethane
ofluoromethane
U Vl
0 0
E rH
O JS
Vl U
,£3 'H
•H Vl
<0.05 <0.05
<0.05 "
0.08 "
0.1 "
<0.05
<0.05
<0.05 "
0.06 "
<0.05 <0.05
<0.05 "
0.1
0.4
0.4 "
0.3
0.3
0.2
01
T3
• rl
01 Vl
01 73 0
*O -H i— 1
•H Vl J3
E O CJ
0 r-l
VI XI 01
M CJ d
Ol
rH i— 1 i— 1
4-> 4-1 4-1
01 01 01
y] y* y*
<0.05 <0.05 <0.05
II It II
M 11 11
tt tt tt
tt It It
It 11 11
t! tt It
tt It tt
<0.05 <0.05 <0.05
ti ti ii
It t! tt
tl It II
It tt II
tt II II
M II tt
II tt tt
hane
loroethane
4-> _C
0) u
O -i-l
IH O
O 1
rH rH
JS
CJ rH
<0.05 <0.05
It If
tt II
It tt
II tf
t! tt
tt It
II II
<0.05 <0.05
u it
it ti
tt ti
M ti
u M
it it
tt 1!
loroethane
a
u
•H
O
CM
<0.05
<0.05
6.0
5.1
4.6
5.0
4.4
2.4
<0.05
<0.05
2.6
4.6
4.2
4.4
4.6
3.8
etrachloride
g«4
O
VI
nt
<0.05
"
"
M
"
11
it
"
<0.05
0.4
<0.05
0.2
<0.05
0.2
0.1
0.07
ichloroethane
VI
E-i
1
i — i
t-H
-
0.2
5.5
3.0
3.4
3.6
3.0
4.2
0.4
0.1
0.3
0.2
0.3
0.2
0.2
0.2
0.08
azene
lorobutane
01 -C
,JQ 0
O T-l
n a
O 1
I-H *sl*
<0.05 <0.05
tt 11
tl tt
II II
tt 11
II tl
II M
tt tt
<0.05 <0.05
II tt
II It
tt 11
tt tt
It tt
tl II
It 11
2-Dichloroethylene
loropropane
** '"i
rH O
1 *r-f
a Q
<0 O">
<0.05 <0.05
tf II
tt tt
tt tf
tt 11
II It
tf tt
It II
<0.05 <0.05
11 It
tt II
II II
tt tt
II tt
ft It
tt II
retrachloroethane
•
CM
CM
rH
<0.05
tt
11
tt
II
11
It
II
<0.05
tt
tt
II
tl
ft
tl
M
loropropane
cj
u
Q
CM
<0.05
tl
It
II
II
tt
ft
11
<0.05
It
It
tt
tt
It
tt
tt
loroethylene
r*
U
b
rH
<0.05
it
tt
u
tt
tt
u
<0.05
II
II
tl
tf
tt
It
tf
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES (pg/1) (Continued)
Performed by TVA Laboratory Branch
i
H
(jo
Shawnee 11/6/79
Lab Blank
Trip Blank
Intake
Inlet
Outlet- 1
Outlet-2
Outlet-3
Intake
o
o
0
rH
"
<0.05
0.08
0.5
5.2
4.8
4.6
0.5
*
o
o
e
0
PQ
<0.05
"
n
it
M
n
it
*
loromethane
jS
u
o
B
O
0)
<0.05
<0.05
5.0
3.9
1.0
5.6
2.5
*
chloromethane
'H
T3
O
E
O
SH
PQ
<0.05
<0.05
<0.05
0.8
0.5
0.6
<0.05
*
chloromethane
o
o
S-l
^
o
<0.05
<0.05
0.2
0.3
0.2
0.2
0.1
*
rofluorome thane
Bromide
o
i— 1 t-H
fi >*
o ji
•H 4->
M Ol
H S
<0.05 <0.05
n ii
M ti
M ti
n ti
n n
n M
* *
Chloride
i— i
JS
4-1
Ol
<0.05
it
it
it
ii
n
"
*
ne Chloride
Ol
r-l
fj
4-1
01
<0.05
tt
11
"
n
"
ti
*
01
ti
to
4-1
01
0
S-l
o
r— 1
U
<0.05
II
M
tt
H
11
11
*
hloroethane
u
•H
Q
1
I— 1
1 — 1
<0.05
<0.05
0.1
<0.05
<0.05
<0.05
<0.05
*
hloroethane
u
•H
O
1
tN
i— 1
<0.05
<0.05
4.1
5.9
5.2
5.4
3.7
*
Tetrachloride
ti
0
-Q
S-l
tO
o
<0.05
<0.05
0.2
0.2
<0.05
0.1
0.09
*
richloroethane
f-4
1
I— 1
~
T— 1
1 1
<0.05
0.1
0.1
0.2
<0.05
<0.05
0.2
*
enzene
^>
o
S-<
o
r— i
o
<0.05
II
tt
tt
II
II
11
*
hlorobutane
u
•H
Q
1
^T
i—l
<0.05
11
II
II
tt
tt
11
*
,2-Dichloroethylene
i-H
1
CO
rt
Co
4->
<0.05
M
n
tt
tt
n
n
*
hloropropane
u
b
'
CO
rH
<0.05
It
It
11
11
M
II
*
:-Tetrachloroethane
CN
ci
**
rH
<0.05
M
It
It
tl
It
It
*
:hloropropane
w
'H
Q
C"J
rH
<0.05
It
It
tt
11
11
II
*
:hloroethylene
w
Q
'
i— i
<0.05
<0.05
0.5
0.4
<0.05
0.2
0.2
*
*Sample broken in transit
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES* (jJg/1)
Kingston 9/11/79
Trip Blank
Inlet-1
Outlet-2
Outlet-3
Allen 9/25/79
Trip Blank
Inlet-1
Outlet-2
Outlet-3
Shawnee 10/2/79
Trip Blank
Intake
Inlet-1
Outlet-2
Outlet-3
Outlet-3 + 20 ppb
Shawnee 11/6/79
Trip Blank3
Inlet-1
Outlet-2
Outlet-3
Outlet-3
Outlet-3
Outlet-3
Lab Blank
Chloride
i— t
cu
4
6
7
6
11
6
6
10
10
8
12
9
7
32
<50
<50
<50
<50
<50
<50
<50
<50
}fluoromethane
Vl
0
1 — 1
• H
O
19
15
12
17
21
19
17
10
22
14
18
17
29
53
<20
<20
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<20
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<20
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Bromide
i — i
cu
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<10
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17
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cu
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5.
16
12
22
23
36
<1.
5.
4.
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cotluoromethane
o
-4
a
u
Vl
H
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15
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6
1
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4
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u
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3
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3
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le Chloride
cu
1 — 1
4-1
CU
s:
35.0
11.9
13.4
12.7
31.1
20.7
11.5
5.8
160
12
15
16
17
31
37.4
1.5
6.8
1.5
56.6
0.1
0.1
1.1
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i
CO
Vl
4-1
II
0.1
0.1
0.1
0.1
0.6
0.1
0.1
0.1
0.1
18.6
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0.1
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0.1
0.1
0.6
0.1
0.1
0.2
0.3
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richloroethane
E-i
1
CNl
-
-------
SUMMARY OF VOLATILE HALOGENATED ORGANICS ANALYSES* (pg/1) (Continued)
OJ
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O
i — 1
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4-)
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^
T— 1
•^
-------
SUMMARY OF SEMIVOLATILE HALOGENATED ORGANICS ANALYSES* (pg/1)
Performed by TVA Laboratory Branch
Plant
2-Chloronapthalene
1,2-Dichlorobenzene
2-Chlorophenol
Kingston (9/11/79)
Intake
Inlet
Outlet
Allen (9/25/79)
Intake
Inlet
Outlet
Allen (11/27/79)
Intake
Inlet
Outlet
1.2
1.0
2.0
1.8
<10.0
79.0
<10.0
-------
APPENDIX B
DATA FOR PRECURSORS, AMINO ACIDS,
AND WATER QUALITY FOR ALL PLANTS
B-l
-------
SUMMARY OF PRECURSORS ANALYSES*
ro
Kingston
Kingston Blank
Allen
Allen Blank
Kingston
Kingston Blank
Allen
Allen Blank
Shawnee
Shawnee Blank
Kingston
Kingston Blank
Allen
Allen Blank
Shawnee
Shawnee Blank
Kingston
Kingston Blank
Allen
Allen Blank
Kingston
Kingston Blank
Allen
Allen Blank
Date
8-21
8-21
9-11
9-25
10-2
10-10
10-16
11-6
11-14
11-27
12-18
12-11
Br"
(Mg/D
116
280
300
61.0
172
60.0
225
60.7
168
63.0
112
63.0
670
62.2
46.4
<40
<40
<40
99.8
<40
<40
<40
95.8
<40
NH3
(pg/D
70.7
32.2
9.2
<8.5
16.1
9.0
19.6
<8.5
23.0
<8.5
18.7
<8.5
19.6
<8.5
<8.5
<8.5
8.2
<8.5
159.8
<8.5
25.5
17.0
204
<8.5
Natural
Color
(mg Pt/1)
0.5
0.0
insufficient
sample
0.6
0.0
3.2
0.0
1.5
0.0
0.8
0.0
1.9
0.0
0.7
0.0
0.5
0.0
3.0
0.0
0.4
0.0
1.8
0.0
Polyhydroxy-
benzenes
(mg/1)
2.6
0.0
6.5
0.6
3.9
0.0
5.0
0.0
25.5
0.0
2.3
0.0
5.4
0.0
2.4
0.0
0.9
0.0
4.5
0.0
2.4
0.0
3.3
0.0
Humic
acids
(rag/1)
1.6
0.0
0.2
0.0
0.5
0.0
1.5
0.0
1.6
0.0
1.5
0.0
0.8
0.0
1.0
0.0
0.8
0.0
1.5
0.0
0.5
0.0
1.4
0.0
Fulvic
acids
(rag/1)
1.1
0.0
0.5
0.0
0.6
0.0
0.7
0.0
0.6
0.0
0.4
0.0
1.2
0.0
0.5
0.0
0.5
0.0
1.5
0.0
0.4
0.0
1.3
0.0
^'Performed by Battelle-Colurabus laboratories.
-------
SUMMARY OF AMINO ACID ANALYSES * ((Jg/D
Sample
Kingston
Blank
Allen
Blank
Kingston
Blank
Allen
W Blank
i
(JO
Shawnee
Blank
Kingston
Blank
Allen
Shawnee
Kingston
Allen
Kingston
Allen
Blank
8/21/79
8/21/79
/
9/11/79 )
(
9/25/79
10/2/79
10/10/79
10/16/79
11/6/79
11/14/79
11/27/79
12/18/79
12/11/79
13
•H
U
U
•H
4-1
to
ft
W
<
2.0
1.1
0.5
f
• Not
0.8
<0.5
2.2
0.8
<0.5
<0.5
<0.5
0.5
1.3
0.6
2.8
0.6
2.5
Ol
d
•H
d
o
01
t_c^
E-H
1.0
0.7
0.8
Analyzed
0.5
<0.5
1.6
<0.5
<0.5
<0.5
<0.5
<0.5
2.7
<0.5
1.8
<0.5
0.9
Ol
d
•H
S-l
01
3.7
3.0
2.2
Due
1.4
1.2
7.2
1.7
1.6
0.6
1.1
1.3
13.4
1.2
9.2
1.2
1.8
•H
U
CO
O
•H
B
CO
a
T— 1
0
1.1
0.6
<0.5
Ol
d
i— i
o
H
EM
1.6
<0.5
0.8
to Breakage
1.1
<0.5
1.8
<0.5
<0.5
<0.5
<0.5
0.5
0.7
0.8
1.3
<0.5
2.5
<0.5
<0.5
0.6
<0.5
<0.5
<0.5
<0.7
<0.5
2.1
<0.5
0.9
<0.5
0.9
V
d
•H
U
r-H
O
3.2
1.6
1.3
•H
r— 1
CO
1.7
0.6
<0.5
nine
o
•H
4-1
O>
<0.5
<0.5
<0.5
d
•H
U
^
!-*
3.0
1.9
2.8
d
CO
01 .d
•H O
d 4-1
•H ft
oo K
^1 ^4
< EH
<0.5
<0.5
<0.5
01
d oi
•H d
OO -H
CO E
S-l CO
CO 4-1
W i— 1
-------
SUMMARY WATER QUALITY DATA
Performed by TVA Laboratory Branch
Organic
Nitrogen
Plant
Allen
Kingston
Shawnee
Date
6/5/79
6/19/79
7/10/79
8/7/79
8/21/79
9/25/79
10/16/79
11/27/79
12/11/79
6/26/79
7/10/79
8/7/79
8/21/79
9/11/79
10/10/79
11/14/79
12/18/79
6/12/79
6/26/79
7/24/79
8/14/79
10/2/79
11/6/79
mg/£
0.34
0.17
0.26
0.70
0.27
0.26
0.21
0.40
0.34
0.23
0.10
0.07
0.14
0.12
0.22
0.10
-
0.12
0.14
0.16
0.12
0.18
0.11
NH3
mg/£
0.10
0.13
0.32
0.02
0.04
0.02
0.05
0.32
0.15
0.11
0.06
0.03
0.02
0.02
0.03
0.01
0.03
0.06
0.06
0.04
0.06
0.01
0.03
N02/N03
mg/£3
1.0
1.4
1.4
1.4
-
1.4
1.4
0.85
0.94
0.51
0.42
0.48
0.79
0.43
0.47
0.19
0.31
0.67
0.37
0.15
0.34
0.44
0.36
TOC
mg/S,
7.1
6.0
8.6
5.4
5.2
6.6
5.2
6.6
5.0
2.6
2.2
2.4
2.4
2.9
4.1
2.2
2.0
4.0
3.6
4.3
4.4
5.8
3.0
Total
Alkalinity TSS
mg/S,
55
70
98
100
110
97
96
74
78
80
59
79
90
96
75
-
69
83
51
51
68
56
60
mg/S,
99
30
15
14
14
11
11
29
10
29
25
20
15
13
11
-
9
26
80
34
41
39
28
Specific Total
Conductivity Fe
mmho
156
240
340
360
340
320
310
340
240
210
170
210
220
240
190
45
180
180
160
140
290
150
150
M8/£
1400
900
1500
1100
660
1800
1100
1000
1700
390
600
1800
620
480
550
700
410
1100
1800
650
1700
690
730
Ca
mg/H
11
19
39
36
35
35
30
35
31
25
22
26
28
32
17
6.7
26
25
19
16
22
21
21
Mg
mg/S,
5.7
8.2
13.0
12.0
11.0
13.0
12.0
7.9
8.4
7.4
5.8
5.7
8.0
8.9
6.0
1.8
7.0
5.9
4.3
3.3
6.0
4.5
3.7
Hardness
mg/S,
_
81
150
140
13
-
-
93
110
93
74
88
100
116
67
24
94
87
65
54
80
71
68
pH
7.3
7.3
7.5
7.4
7.7
-
7.3
7.3
7.1
7.6
7.2
7.3
7.4
8.0
7.5
7.0
7.9
7.3
7.7
7.4
7.3
7.4
7.3
-------
SUMMARY WATER QUALITY DATA (Continued)
Performed by TVA Laboratory Branch
bd
i
VJl
Plant
Allen
Kingston
Shawnee
Date
6/5/79
6/19/79
7/10/79
8/7/79
8/21/79
9/25/79
10/16/79
11/27/79
12/11/79
6/26/79
7/10/79
8/7/79
8/21/79
9/11/79
10/10/79
11/14/79
12/18/79
6/12/79
6/26/79
7/24/79
8/14/79
10/2/79
11/6/79
Chlorine
Dosage
Calculated
mg/2
0.97
1.15
2.10
1.53
1.53
1.13
1.04
0.80
1.15
0.60
0.60
0.86
0.86
0.79
1.13
1.05
1.11
0.95
1.10
0.85
0.58
0.75
0.61
Cooling
Water
Rate
gpm
102,897
108,541
108,941
135,575
135,575
125,596
112,446
124,261
86,673
110,619
110,619
106,039
106,039
106,039
103,364
111,396
104,634
125,659
116,040
88,135
122,831
110,584
121,930
Free Residual Chlorine
Total Residual Chlorine
( -. mg/S. f^^ fn>l rag/A fo^ Temperature °F
Inlet
0.09
0.20
0.23
0.17
0.16
0.20
0.17
0.11
0.18
0.33
0.06
0.24
0.21
0.30
0.58
0.49
1.12
0.51
0.46
0.29
0.09
0.33
0.12
Outlet^'
0.11
0.24
0.12
0.25
0.12
0.14
0.13
0.10
0.12
0.30
0.13
0.36
0.22
0.19
0.46
0.75
0.70
0.35
0.31
0.20
0.12
0.27
0.15
Inlet ^ '
0.16
0.44
0.50
0.32
0.32
0.41
0.31
0.45
0.65
0.49
0.35
0.40
0.32
0.55
0.66
0.78
1.61
0.63
0.63
0.36
0.25
0.59
0.27
Outlet^ '
0.22
0.40
0.40
0.13
0.29
0.26
0.22
0.41
0.59
0.46
0.38
0.52
0.36
0.45
0.69
0.85
0.88
0.58
0.55
0.33
0.22
0.47
0.29
Intake
70
75.9
78.8
83.5
82.2
73.4
51.8
52
46.4
70
69
66
68
68
64
51
46
71
74
81
77
66
59
Inlet
70.0
75.9
79.3
83.5
82.2
73.0
65.4
53.5
46.5
70
70
72
71
74
68
52
47
72
77
85
80
73
61
Outlet
92.2
95.5
97.9
100.3
93.8
90.5
83.9
63.7
54.8
86
82
80
88
88
83
64
60
84
95
91
95
86
74
(a)
Average measurement.
-------
APPENDIX C
QUALITY ASSURANCE DATA
C-l
-------
QUALITY ASSURANCE DATA
Careful quality assurance practices were followed in the conduct of
the analyses. Replicates were used to determine precision and spikes were
used to verify accuracy. Battelle-Columbus quality assurance for precursors
data are presented in Vigon and Stanford (1980). TVA's quality assurance
program for halogenated organics is discussed in this section.
Precision for the extraction of volatile organic analyses was moni-
tored by analyzing a surrogate standard. A single surrogate, 1,4-dichlo-
robutane, was used from June 15 through September 15, 1979. Every tenth
sample (or one sample in each batch of samples, if less than ten samples
analyzed) was spiked in duplicate with the surrogate and analyzed. Warn-
ing and control limits for precision were generated by determining the
standard deviation of the RSD's for the first seven sets of duplicate
data. Accuracy was assessed by comparing percent bias values for the
1,4-dichlorobutane surrogate to a mean value which was obtained by the
same day analysis of 20 aliquots of the 1,4-dichlorobutane solution.
However, surrogate data generated from early August through September 15,
1979 are suspect because the 1,4-dichlorobutane surrogate likely vaporized
from its deionized water matrix during this period of abnormally high
temperature in the laboratory. Data for samples during this interval have
been judged satisfactory because standards were prepared in a methanol
matrix rather than an aqueous matrix and previously constructed calibrated
curves checked within limits.
Two surrogate compounds, bromochloromethane and l-chloro-2-bromo-
propane were used to monitor the precision and accuracy of volatile organic
analyses completed after September 15, 1979. These two surrogates more
closely approximated the volatility of components that were being detected
in the aqueous samples. Warning and control limits for precision obser-
vations were generated by determining the standard deviation of the rela-
tive standard deviations on ten sets of duplicate analyses done on
November 9, 1979. Accuracy was assessed by comparing the percent bias
values for the two surrogates to a mean percent bias value determined by
the replicate analyses on the November 19, 1979 date.
Accuracy of volatile organic analyses was also assessed by analyzing
EPA reference samples. EPA sample No. WS 1276—a set of two samples of
different concentrations—was submitted and analyzed as an unknown on
June 7, 1979, and November 9, 1979. Each analysis was done by a different
analyst.
Semivolatile chlorinated organic analyses were monitored by duplicate
spiking of every tenth sample with a representative compound from both the
acid extractable and base-neutral fractions. Precision and accuracy of
the acid extractable analyses were assessed by spiking the sample with
2,4-dichlorophenol. Warning and control limits for precision were gene-
rated by determining the standard deviation of the relative standard
deviations for the first seven sets of duplicate data. Warning and
control limits for accuracy were generated by determining the standard
deviation of the percent bias values for the first seven pieces of
2,4-dichlorophenol-spiked data.
C-2
-------
Precision and accuracy of the base-neutral analyses were assessed by
spiking the sample with hexachlorobenzene. Warning and control limits for
precision were generated by determining the standard deviation of the
relative standard deviations for the first seven sets of duplicate data.
Warning and control limits for accuracy were generated by determining the
standard deviation of the percent bias values for the first seven sets of
hexachlorobenzene-spiked data.
The quality assurance data for volatile organic analyses are shown
graphically in Figures C-l to C-3 and all data are tabulated in Table C-2
to C-13. Analysis of the EPA standards is shown in Table C-l.
One important factor which enters into the statistical analysis is
that the analytical error of the dependent variable must be small relative
to the range of that variable. If this is not the case then the signifi-
cance of the statistical procedures is questionable. For the semivolatile
compounds the analytical accuracy is within ±10 percent. This is not
expected to affect the statistical analyses for chloroform since the chlo-
roform concentrations varied from 0.05 to 11.0 pg/1.
Finally, a set of tests were run to determine holding times for each
of three analytes — chloroform, dichlorobromomethane, and chlorodibromome-
thane. At an average concentration of 23 Mg/1 chloroform exhibited at
10 percent relative standard deviation. Dichlorobromomethane averaged
6.3 (Jg/1 and was the least variable at 4.2 percent relative standard devia-
tion. Chlorodibromomethane was the most variable with an 11.3 percent
relative standard deviation, but also had the lowest average concentration
of 0.70 fJg/1. None of the three compounds exhibited a tendency toward
lower concentrations with time (Figure C-4). It was concluded that the
volatile halogenated organics when properly stored could be kept for
periods up to three weeks without degradation or volatility losses.
C-3
-------
20
10
o
i
t/3
<
m -10
-20
-30
WARNING LINE (W. L.)=±4% BIAS
CONTROL LINE (C. L.) = ±8% BIAS
G-0
SEE TEXT FOR DISCUSSION OF
THIS PERIOD *
-40
6/6/79
I
I
I
I
6/I4/T9 6/28/79
7/16/79 7/30/79
SAMPLING DATE
8/14/79 9/13/79
Figure C-l. Accuracy chart (1,4 dichlorobutane surrogate)
for volatile halogenated organics
-------
o
vn
20
BROMOCHLOROMETHANE
0—O
10
to
m
-10
U.C.L.
U.W.L.
L.W.L.
0—0
L.C.L.
-20
WARNING LINE (W.L.) = ±4.9% BIAS
CONTROL LINE (C.L.)=±9.8% BIAS
-30
11/9/79
_L
_L
11/28/79 12/10/79
SAMPLING DATE
20
10
-10
-20
-30
I-CHLORO-2-BROMOPROPANE
U.C.L.
U.W.L.
©
0 — O
O
WARNING LINE (W. L.) =±3.6% BIAS
CONTROL LINE (C. L.) = ±7.2% BIAS
_L
JL
1/19/79 11/28/79 12/10/79
SAMPLING DATE
Figure C-2. Accuracy chart (bromochloromethane and l-chloro - 2-bromopropane)
for volatile halogenated organics
-------
o
C.V
10
0
m
#
-10
-20
-an
BROMOCHLOROMETHANE
- -
U.C.L.
Q— .0 U.W.L.
\) Q
L.W. L.
L.C.L.
- —
_
WARNING LINE (W.L.) = ±3.0 % BIAS
CONTROL LINE (C.L.) =±6.0% BIAS
1 1
20
11/9/79 12/6/79
SAMPLING DATE
10
CO
<
m
-10 -
-20 -
-30
I -CHLORO-2-BROMOPROPANE
©
U.C.L.
U.W.L.
O—0—©
L.W.L.
L.C.L.
WARNING LINE (W.L.) =±5.0% BIAS
CONTROL LINE (C. L. ) = ± 10.0 % BIAS
1/9/79 12/6/79
SAMPLING DATE
Figure C-3. Precision chart (bromochloromethane and I-chloro - 2-bromopropane)
for volatile halogenated organics
-------
TABLE C-l. ANALYSIS OF EPA REFERENCE STANDARD WS 1276*
(Volatile Halogenated Organics)
o
Parameter
Chloroform
Chlorodibromo-
me thane
Dichlorobromo-
me thane
Bromoform
Date
6/7
11/9
6/7
11/9
6/7
11/9
6/7
11/9
EPA True
Value, pg/1
9.1
68
9.1
68
2.7
17.2
2.7
17.2
1.2
11.9
1.2
11.9
2.8
14.2
2.8
14.2
Measured
Value, (Jg/1
10
75
9.0
54
2.6
19
2.0
18
1.6
20
2.3
16
2.8
16
3.0
17
% Recovery
110
110
99
79
96
110
111
105
13
166
193
134
100
113
107
120
% Bias
+10
+10
-1
-21
-4
+10
+11
+5
+33
+66
+93
+34
0 -
+13
+7
+20
*TVA Laboratory Branch data.
-------
TABLE 02. QUALITY ASSURANCE DATA FOR PRECURSORS
Spiked
Bromide 399.6
Ammonia 85.0
Natural Color 10.0
25.0
Polyhydroxy- 1 . 0
benzenes 6.0
Mg Br/1
Mg NH3/1
mg/Pt/1
mg Pt/1
mg/1
mg/1
0 20 mg/1
i
Humic Acids 1.1 mg/1
Fulvic Acids 0.6
mg/1
375.6
85.0
10.3
24.7
0.8
6.5
20.3
0.8
0.0
359.6
83.3
10.4
24.8
1.2
5.6
17.8
0.8
0.3
Found
391.6
85.0
10.4
24.9
0.6
4.0
18.0
0.4
0.4
359.6
86.7
10.4
24.9
0.7
5.7
12.2
0.9
0.4
367.6
85.0
10.4
25.0
0.5
5.4
14.7
0.7
0.7
359.6
86.7
10.4 10.4
24.8 24.8
1.4
5.6
16.6
0.4
0.4
Mean
368.9
85.3
10.4
24.8
0.9
5.5
16.6
0.7
0.4
Recovery
-8%
0.4%
4%
-0.8%
-13.3%
8.9%
-17.0%
-39.4%
-38.9%
s
11.69
1.17
0.035
0.090
0.325
0.743
2.584
0.197
0.205
RSD
3.2%
1.4%
0.3%
0.4%
37.5%
13.6%
15.6%
29.6%
56.0%
Calculation of recoveries from these averages may give slightly different results than those shown due to round-off.
These recovery factors have not been applied to the data.
-------
TABLE C-3. QUALITY ASSURANCE DATA FOR AMINO ACID ANALYSES
O
•H
U
OJ
o d
•H >H
4-> d
S-l O
to
S-l 3
0) r-l
w o
tU
d
•H
i— 1
O
Ol
T— 1
ca
, — i
tU
d
•H
d
tO
T— 1
, to S M i-q
tu
d
•H
w
o
VI
H*
anine
,—4
to
i— 1
t>>
d
"• S-l
h^I
("}. ^
W i-H
-------
TABLE C-4. ACCURACY CHART FOR SEMIVOLATILES (BASE-NEUTRALS)
Parameters Hexachlorobenzene Date Started 6-16-79 Date Terminated 8-2-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
6-16-79
6-16-79
6-20-79
6-20-79
6-20-79
6-20-79
7-10-79
7-10-79
7-11-79
7-11-79
7-12-79
7-12-79
7-13-79
7-13-79
7-24-79
7-24-79
7-24-79
7-24-79
8-2-79
8-2-79
|Jg/l jjg/1
Bkg. Added
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 10
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
M8/1
Obs.
17.2
9.4
12.
24.
9.6
14.6
2.2
3.2
4.0
5.4
4.6
4.8
8.4
8.0
28.
47.
46.
42.
52.
46.
M8/1
Rec.
17.2
9.4
12.
24.
9.6
14.6
2.2
3.2
4.0
5.4
4.6
4.8
8.4
8.0
28.
47.
46.
42.
52.
46.
Rec.
172
93
120
240
96
146
22
32
40
54
46
48
84
80
47
78
77
70
87
77
% Bias
(% Rec.
-100)
72
-7
20 1 s.d. = 49%
140 2 s.d. = 98%
-4
46
-78
-68
-60
-46
-54
-52
-16
-20
-53
-22
-23
-30
-13
-23
c-io
-------
TABLE C-4. ACCURACY CHART FOR SEMIVOLATILES (BASE-NEUTRALS)
(Continued)
Parameters Hexachlorobenzene Date Started 8-7-79 Date Terminated 11-6-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
8-7-79
8-7-79
8-28-79
8-28-79
9-18-79
9-18-79
9-18-79
9-18-79
9-19-79
9-19-79
9-21-79
9-21-79
10-30-79
10-30-79
11-1-79
11-1-79
11-1-79
11-1-79
11-6-79
11-6-79
Mg/1 MgA
Bkg. Added
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
<1.0 60
Mg/1
Obs.
19.
16.4
48.
46.
46.
47.2
48.
46.
54.6
48.
54.
54.
45.8
47.4
48.2.
48.4
47.6
50.
54.
54.
Mg/1
Rec.
19.
16.4
48.
46.
46.
47.2
48.
46.
54.6
48.
54.
54.
45.8
47.4
48.2
48.4
47.6
50.
54.
54.
Rec.
32
27
80
77
77
79
80
77
91
80
90
90
76
79
80
81
79
83
90
90
% Bias
(% Rec.
-100)
-68
-73
-20
-23
-23
-21
-20
-23
-9
-20
-10
-10
-24
-21
-20
-19
-21
-17
-10
-10
C-ll
-------
TABLE C-4. ACCURACY CHART FOR SEMIVOLATILES (BASE-NEUTRALS)
(Continued)
Parameters Hexachlorobenzene Date Started 11-6-79 Date Terminated 1-17-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date Bkg.
11-6-79 <1.0
11-6-79 <1.0
12-18-79 <1.0
12-18-79 <1.0
12-18-79 <1.0
12-18-79 <1.0
12-18-79 <1.0
12-18-79 <1.0
1-14-80 <1.0
1-14-80 <1.0
1-17-80 <1.0
1-17-80 <1.0
H8/1
Added
60
60
60
60
60
60
60
60
60
60
60
60
Mg/1
Obs.
52.
50.8
42.
50.
41.
45.6
34.2
47.6
40.2
53.6
47.2
48.4
Mg/1 %
Rec. Rec.
52. 87
50.8 85
42. 70
50. 83
41. 68
45.6 76
34.2 57
47.6 79
40.2 67
53.6 89
47.2 79
48.4 81
% Bias
(% Rec.
-100)
-13
-15
-30
-17
-32
-24
-43
-21
-33
-11
-21
-19
C-12
-------
TABLE C-5. ACCURACY CHART FOR SEMIVOLATILES (ACID EXTRACTABLES)
Parameters 2,4-Dichlorophenol Date Started 6-19-79 Date Terminated 8-2-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
6-19-79
6-19-79
6-20-79
6-20-79
6-20-79
6-20-79
7-10-79
7-10-79
7-11-79
7-11-79
7-12-79
7-12-79
7-13-79
7-13-79
7-24-79
7-24-79
7-24-79
7-24-79
8-2-79
8-2-79
Mg/1 |Jg/l
Bkg. Added
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 10
<10 60
<10 60
<10 60
<10 60
<10 60
<10 60
M8/1
Obs.
9.4
12.
3.2
3.2
5.4
4.8
1.6
1.6
0.4
0
0.8
0.8
4.0
8.6
34.
36.
36.
34.
26.
26.
M8/1
Rec.
9.4
12.
3.2
3.2
5.4
4.8
1.6
1.6
0.4
0
0.8
0.8
4.0
8.6
34.
36.
36.
34.
26.
26.
Rec.
94
120
32
32
54
48
16
16
4
0
8
8
40
86
57
60
60
57
43
43
% Bias
(% Rec.
-100)
-6
20
-68
-68 1 s.d. = 28%
-46 2 s.d. = 56%
-52
-84
-84
-96
-100
-92
-92
-60
-14
-43
-40
-40
-43
-57
-57
C-13
-------
TABLE C-5. ACCURACY CHART FOR SEMIVOLATILES (ACID EXTRACTABLES)
(Continued)
Parameters 2,4-Dichlorophenol Date Started 8-7-79 Date Terminated 11-6-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Mg/1
Date Bkg.
8-7-79 <10
8-7-79 <10
8-28-79 <10
8-28-79 <10
9-18-79 <10
9-18-79 <10
9-18-79 <10
9-18-79 <10
9-19-79 <10
9-19-79 <10
9-21-79 <10
9-21-79 <10
10-30-79 <10
10-30-79 <10
11-1-79 <10
11-1-79 <10
11-1-79 <10
11-1-79 <10
11-6-79 <10
11-6-79 <10
Mg/1
Added
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
Mg/1
Obs.
24.
28.
34.
40.
28.
38.
45.
41.
42.6
54.8
44.
37.6
42.4
53.2
32.4
28.2
31.
34.4
45.
34.6
Mg/1
Rec.
24.
28.
34.
40.
28.
38.
45.
41.
42.6
54.8
44.
37.6
42.4
53.2
32.4
28.2
31.
34.4
45.
34.6
Rec.
40
47
56
67
47
64
75
68
71
91
72
63
71
88
54
47
52
57
75
58
% Bias
(% Rec.
-100)
-60
-53
-44
-33
-53
-36
-25
-32
-29
-9
-28
-37
-29
-12
-46
-53
-48
-43
-25
-42
C-lk
-------
TABLE C-5. ACCURACY CHART FOR SEMIVOLATILES (ACID EXTRACTABLES)
(Continued)
Parameters 2,4-Dichlorophenol Date Started 11-6-79 Date Terminated 1-17-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Mg/1 MS/1 pg/1 (Jg/1 %
Date Bkg. Added Obs. Rec. Rec.
11-6-79 <10 60 31.6 31.6 53
11-6-79 <10 60 24. 24. 41
12-12-79 <10 60 30.6 30.6 51
12-12-79 <10 60 51.8 51.8 86
12-12-79 <10 60 43.6 43.6 73
12-12-79 <10 60 40.8 40.8 68
12-12-79 <10 60 39.8 39.8 66
12-12-79 <10 60 39.4 39.4 66
1-17-80 <10 60 37.6 37.6 63
1-17-80 <10 60 34.8 34.8 58
% Bias
(% Rec.
-100)
-47
-59
-49
-14
-27
-32
-34
-34
-37
-42
c-15
-------
TABLE C-6. ACCURACY CHART FOR VOLATILE HOLOGENATED ORGANICS
CH2ClBr
Parameters Bromochloromethane Date Started 11-9-79 Date Terminated 11-9-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
M8/1
Bkg.
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
M8A
Added
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
MSA
Obs.
2.47
2.72
2.50
2.57
2.50
2.47
2.57
2.38
2.30
2.16
2.35
2.26
2.28
2.85
2.90
2.65
2.58
2.46
2.57
2.44
M8/1
Rec.
2.47
2.72
2.50
2.57
2.50
2.47
2.57
2.38
2.30
2.16
2.35
2.26
2.28
2.85
2.90
2.65
2.58
2.46
2.57
2.44
%
Rec.
99
109
100
103
100
99
103
95
92
86
94
90
91
114
116
106
103
98
103
98
% Bias
(% Rec.
-100)
-1
+9
0
+3
0
-1
+3
+5
-8
-14
-6
-10 1 s.d. = 4.9%
-9 2 s.d. = 9.8%
+14
+16
+6
+3
-2
+3
-2
c-16
-------
TABLE C-6. ACCURACY CHART FOR VOLATILE HOLOGENATED ORGANICS
(Continued)
CH2ClBr
Parameters Bromochloromethane Date Started 11-9-79 Date Terminated 12-10-79
Sample % Bias
Number pg/1 pg/1 |Jg/l (JgA % (% Rec.
M Date Bkg. Added Obs. Rec. Rec. -100)
1 11-9-79 <0.05 2.5 2.4 2.4 96 -4
2 11-9-79 <0.05 2.5 2.2 2.2 88 -12
3 11-28-79 <0.05 2.5 2.8 2.8 112 +12
4 11-28-79 <0.05 2.5 2.8 2.8 112 +12
5 12-6-79 <0.05 2.5 2.3 2.3 92 -8
6 12-6-79 <0.05 2.5 2.3 2.3 92 -8
7 12-10-79 <0.05 2.5 2.1 2.1 84 -16
8 12-10-79 <0.05 2.5 2.3 2.3 92 -8
9
10
11
12
13
14
15
16
17
18
19
20
C-17
-------
TABLE C-7. ACCURACY CHART FOR VOLATILE HALOGENATED ORGANICS
CH2ClCHBrCH3
Parameters l-Chloro-2-Bromopropane Date Started 11-9-79 Date Terminated 11-9-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
M8/1
Bkg.
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
M8/1
Added
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
M8/1
Obs.
2.4
2.6
2.5
2.6
2.6
2.5
2.6
2.6
2.2
2.3
2.5
2.3
2.5
2.7
2.7
2.6
2.5
2.5
2.4
2.5
M8/1
Rec.
2.4
2.6
2.5
2.6
2.6
2.5
2.6
2.6
2.2
2.3
2.5
2.3
2.5
2.7
2.7
2.6
2.5
2.5
2.4
2.5
%
Rec.
96
104
100
104
104
100
104
104
88
92
100
92
100
108
108
104
100
100
96
"100
% Bias
(% Rec.
-100)
-4
+4
0
+4
+4
0
+4
+4
-12
-8
0
-8 1 s.d. = 3.6%
0 2 s.d. = 7.1%
8
8
+4
0
0
-4
0
c-18
-------
TABLE C-7. ACCURACY CHART FOR VOLATILE HALOGENATED ORGANICS
(Continued)
CH2ClCHBrCH3
Parameters l-Chloro-2-Bromopropane Date Started 11-19-79 Date Terminated 12-10-79
Sample % Bias
Number jjg/1 jjg/1 pg/1 pg/1 % (% Rec.
M Date Bkg. Added Obs. Rec. Rec. -100)
1 11-19-79 <0.05 2.5 2.4 2.4 96 -4
2 11-19-79 <0.05 2.5 2.3 2.3 92 -8
3 11-28-79 <0.05 2.5 2.4 2.4 96 -4
4 11-28-79 <0.05 2.5 2.5 2.5 100 0
5 12-6-79 <0.05 2.5 2.3 2.3 92 -8
6 12-6-79 <0.05 2.5 2.3 2.3 92 -8
7 12-10-79 <0.05 2.5 2.5 2.5 100 0
8 12-10-79 <0.05 2.5 2.5 2.5 100 0
9
10
11
12
13
14
15
16
17
18
19
20
C-19
-------
TABLE C-8. RESULTS OF EPA REFERENCE SAMPLES - WS 1276
(Volatile Halogenated Organics)
Chloroform, Bromoform,
Dichlorobromomethane,
Parameters Chlorodibromomethane Date Started 6-7-79 Date Terminated 6-7-79
Sample
Number
M Date
1 6-7-79
2 6-7-79
3
4 6-7-79
5 6-7-79
6
7 6-7-79
8 6-7-79
9
10 6-7-79
11 6-7-79
12
13
14
15
16
17
18
19
20
M8/1
EPA % Bias
Sample True |jg/l jjg/1 % (% Rec.
I.D. Value Obs. Rec. Rec. -100) Parameter
#1 9.1 10. 10. 110 10 CHC13
#2 68. 75. 75. 110 10 CHCL3
#1 12. 20. 20. 166 66 CHCl2Br
#2 1.2 1.6 1.6 133 33 CHCl2Br
#1 2.7 2.6 2.6 96 -4 CHClBr2
#2 17.2 19. 19. 110 10 CHClBr2
//I 2.8 2.8 2.8 100 0 CHBr3
#2 14.2 16. 16. 113 13 CHBr3
C-20
-------
TABLE C-8. RESULTS OF EPA REFERENCE SAMPLES - WS 1276
(Volatile Halogenated Organics)
(Continued)
Chloroform, Bromoform,
Dichlorobromomethane,
Parameters Chlorodibromomethane Date Started 11-9-79 Date Terminated 11-9-79
P8/1
Sample EPA
Number Sample True |Jg/l pg/1 %
M Date I.D. Value Obs. Rec. Rec.
1 11-9-79 #1 9.1 9.0 9.0 99
2 11-9-79 #2 68. 54. 54. 79
3
4 11-9-79 #1 1.19 2.3 2.3 193
5 11-9-79 #2 11.9 16. 16. 134
f.
D
7 11-9-79 #1 2.7 3.0 3.0 111
8 11-9-79 #2 17.2 18. 18. 105
9
10 11-9-79 #1 2.8 3.0 3.0 107
11 11-9-79 #2 14.2 17. 17. 120
12
13
14
15
16
17
18
19
20
% Bias
(% Rec.
-100) Parameter
-1 CHC13
-21 CHCL3
+93 CHCl2Br
+34 CHCl2Br
+11 CHClBr2
+5 CHClBr2
+7 CHBr3
+20 CHBr3
021
-------
TABLE C-9. PRECISION CHART FOR SEMIVOLATILES (Base-Neutrals)
Parameters Hexachlorobenzene
Date Started 6-16-79 Date Terminated
11-6-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
6-16-79
6-20-79
6-20-79
7-10-79
7-11-79
7-12-79
7-13-79
7-24-79
7-24-79
8-2-79
8-7-79
8-28-79
9-18-79
9-18-79
9-19-79
9-21-79
11-1-79
11-1-79
11-6-79
11-6-79
M8A
No. 1
17.2
12.
9.6
2.2
4.0
4.6
8.4
28.
46.
52.
19.
48.
47.4
48.
54.6
54.
48.2
47.6
54.
52.
M8/1
No. 2
9.4
24.
14.6
3.2
5.4
4.8
8.0
47.
42.
46.
16.4
46.
47.2
46.
48.
54.
48.4
50.
54.
50.8
Diff.
(di)
7.8
12.
5.0
1.0
1.4
0.2
0.4
19.
4.
6.0
2.6
2.0
0.2
2.0
6.6
0
0.2
2.4
0
1.2
Mean
*• 2 "*
13.3
18.
12.1
2.7
4.7
4.7
8.2
37.5
44.
49.
17.7
47.
47.3
47.
51.3
27.
48.3
48.8
54.
51.4
S.D.
(di x 0.89)
6.9
10.7
4.4
.89
1.2
.178
.356
16.9
3.56
5.3
2.3
1.78
.178
1.78
5.9
0
.178
2.14
0
1.07
%RSD
f -inn")
\ A J. \J\S I
mean
52.2
59.3
36.8 1 s.d. =
33.0 21%
26.5 2 s.d. =
3.8 42%
4.3
45.1
8.1
10.9
13.1
3.8
0.4
3.8
11.5
0
.37
4.4
0
2.1
C-22
-------
TABLE C-9. PRECISION CHART FOR SEMIVOLATILES (Base-Neutrals)
(Continued)
Parameters Hexachlorobenzene Date Started 12-18-79 Date Terminated 1-17-80
Sample
Number (Jg/1 |Jg/l Diff.
M Date No. 1 No. 2 (di)
1 12-18-79 42. 50. 8.
2 12-18-79 41. 45.6 4.6
3 12-18-79 34.2 47.6 13.4
4 1-14-80 40.2 53.6 13.4
5 1-17-80 47.2 48.4 1.2
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Mean ~ „ %RSD
IT -i j_vr i 0.1). or.
,No.l+No.2. ,,. „ „ 00, , SD Q0^
46. 7.12 15.5
43.3 4.1 9.4
40.9 11.9 29.2
46.9 11.9 25.4
47.8 1.07 2.2
C-23
-------
TABLE C-10. PRECISION CHART FOR VOLATILE HALOGENATED ORGANICS
Parameters 1,4-Dichlorobutane Date Started 6-6-79 Date Terminated 9-15-79
Sample
Number
M
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
6-6-79
6-13-79
6-14-79
6-21-79
6-28-79
6-28-79
6-29-79
7-16-79
7-16-79
7-30-79
7-30-79
8-8-79
8-14-79
8-23-79
9-13-79
9-14-79
9-15-79
Mg/1
No. 1
2.26
2.28
2.57
2.40
2.25
2.29
2.26
2.58
2.68
2.58
2.43
2.22
2.18
1.92
1.98
2.00
1.76
Mg/1
No. 2
2.30
2.40
2.54
2.38
2.26
2.19
2.34
2.46
2.67
2.67
2.38
2.22
2.16
1.98
2.10
2.00
1.76
Diff.
(di)
0.04
0.12
0.03
0.02
0.01
0.10
0.08
0.12
0.01
0.09
0.05
0
0.02
0.06
0.12
0
0
Mean
^No.l+No.2^
C 2 J
2.28
2.34
2.56
2.39
2.26
2.24
2.30
2.52
2.68
2.62
2.40
2.22
2.17
1.95
2.04
2.00
I.j76
S.D.
(di x 0.89)
0.036
0.107
0.027
0.018
0.009
0.089
0.071
0.107
0.009
0.080
0.044
0
0.018
0.050
0.107
0
0
%RSD
( s® •« innl
Van x 100J
1.6
4.6
1.0 1 s
0.7
0.4 2 s
4.0
3.1
4.2
0.3
3.0
1.8
0
0.8
2.7
5.2
0
0
.d. =
1.7%
~ 2%
.d. =
3.4%
~ 4%
C-2k
-------
TABLE C-ll. PRECISION CHART FOR SEMIVOLATILES (Acid Extractables)
Parameters 2,4-Dichlorophenol Date Started 6-19-79 Date Terminated 11-6-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
6-19-79
6-20-79
6-20-79
7-10-79
7-11-79
7-12-79
7-13-79
7-24-79
7-24-79
8-2-79
8-7-79
8-28-79
9-18-79
9-18-79
9-19-79
9-21-79
10-30-79
11-1-79
11-1-79
11-6-79
No. 1
9.4
3.2
5.4
1.6
0.4
0.8
4.0
34.
36.
26.
24.
34.
28.
45.
42.6
44.
42.4
32.4
31.
45.
H8/1
No. 2
12.0
3.2
4.8
1.6
0.0
0.8
8.6
36.
34.
26.
28.
40.
38.
41.
54.8
37.6
53.2
28.2
34.4
34.6
Diff.
(di)
2.6
0
0.6
0
0.4
0
4.6
2.0
2.0
0
4.0
6.0
10.
4.0
12.2
6.4
10.8
4.2
3.4
10.4
Mean
,No.l+No.2,
( 2 ->
10.7
3.2
5.1
1.6
0.2
0.8
6.4
35.
35.
26.
26.
37.
33.
43.
48.7
40.8
47.8
30.3
32.7
39.8
S.D.
(di x 0.89)
2.31
0
0.53
0
.40
0
4.1
1.78
1.78
0
3.56
5.34
8.9
3.56
10.8
5.7
9.6
3.73
3.0
9.3
( SD x 100)
I X 1UU 1
mean
21.6
0
10.5 1 s.d. =
0 65%
178. 2 s.d. =
0 130%
64.
5.1
5.1
0
13.7
14.4
27.0
10.8
22.3
14.
20.1
12.3
9.2
23.4
C-25
-------
TABLE C-ll. PRECISION CHART FOR SEMIVOLATILES (Acid Extractables)
(Continued)
Parameters 2,4-Dichlorophenol Date Started 11-6-79 Date Terminated 1-17-80
Sample
Number
M
Date
(jg/1 |jg/l Diff.
No. 1 No. 2 (di)
Mean
.No.l+No.2.
S.D.
(di x 0.89) (
%RSD
SD
mean
x 100)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
11-6-79 31.6 24. 7.6 27.8
12-12-79 30.6 51.8 21.2 41.2
12-12-79 40.8 43.6 2.8 42.2
12-12-79 39.8 39.4 0.4 39.6
1-17-80 37.6 34.8 2.8 36.2
1-17-80 35.8 40.6 4.8 38.2
6.76
18.9
2.49
.356
2.49
4.27
24.3
46.
5.9
2.5
6.9
11.2
C-26
-------
TABLE C-12. PRECISION CHART FOR VOLATILE HALOGENATED ORGANICS
Parameters Bromochloromethane (CH2ClBr) Date Started 11-9-79 Date Terminated 11-9-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-19-79
11-28-79
12-6-79
12-10-79
Pg/1
No. 1
2.47
2.50
2.50
2.57
2.30
2.35
2.28
2.90
2.58
2.57
2.4
2.8
2.3
2.4
Mg/1
No. 2
2.72
2.57
2.47
2.38
2.16
2.26
2.85
2.65
2.46
2.44
2.2
2.8
2.3
2.3
Diff.
(di)
0.25
0.07
0.03
0.19
0.14
0.09
0.57
0.25
0.12
0.13
0.2
0
0
0.1
Mean
C 2 )
2.60
2.54
2.49
2.48
2.23
2.30
2.56
2.78
2.52
2.50
2.3
2.8
2.3
2.4
S.D.
(di x 0.89)
0.22
0.06
0.03
0.17
0.12
0.08
0.51
0.22
0.11
0.12
0.18
0
0
0.09
%RSD
( SD -x inn")
Van x 10UJ
8.5
2.4
1.2
6.9
5.4 1 s.d. =
/•v
3.5 ~ 5%
19.9 2 s.d. =
7.9 ~ 10%
4.4
4.8
7.7
0
0
3.8
C-27
-------
TABLE C-13. PRECISION CHART FOR VOLATILE HALOGENATED ORGANICS
CH2ClCHBrCH3
Parameters 1-Chloro- 2-Bromopropane Date Started 11-9-79 Date Terminated 12-10-79
Sample
Number
M
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Date
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-9-79
11-19-79
11-28-79
12-6-79
12-10-79
Mg/1
No. 1
2.4
2.5
2.6
2.6
2.2
2.5
2.5
2.7
2.5
2.4
2.4
2.4
2.3
2.5
M8/1
No. 2
2.6
2.6
2.5
2.6
2.3
2.3
2.7
2.6
2.5
.25
2.3
2.5
2.3
2.5
Diff.
(di)
0.2
0.1
0.1
0
0.1
0.2
0.2
0.1
0
0.1
0.1
0.1
0
0
Mean
,No.l+No.2.,
I 2 )
2.5
2.6
2.6
2.6
2.2
2.4
2.6
2.6
2.5
2.4
2.4
2.4
2.3
2.5
S.D.
(di x 0.89)
0.18
0.09
0.09
0
0.09
0.12
0.18
0.09
0
0.09
0.09
0.09
0
0
%RSD
( -,r 1
X 1
mean
7.2
0.3
0.3
0
4.0
7.4
6.9
3.4
0
3.6
3.8
3.6
0
0
00)
1 s.d. =
E 3.0%
2 s.d. =
~6%
C-28
-------
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-------
TECHNICAL REPORT DATA
(Pleat read Instructions on the reverse before completing}
REPORT NO
EPA-600/7-81-094
2.
3. RECIPIENT'S ACCESSION- NO.
TITLE AND SUBTITLE
Halogenated Organics Study for Allen, Kingston, and
Shawnee Steam Plants
,. REPORT DATE
May 1981
I. PERFORMING ORGANIZATION CODE
AUTHORS c.V.Seaman,H.B.Flora II,L.O.Hill (TVA);
B.W. Vigon, T.B.Stanford, M.D. Hunter (Battelle)
. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
TVA
1140 Chestnut Street, Tower II
Chattanooga, Tennessee 37401
10. PROGRAM ELEMENT NO.
INE624A
11. CONTRACT/GRANT NOT
IAG-D5-E721
2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final- 6/79 - 2/81
14. SPONSORING AGENCY CODE
EPA/600/13
s. SUPPLEMENTARY NOTES IERL-RTP project officer is Julian W. Jones, Mail Drop 61,
919/541-2489.
6. ABSTRACT
The report summarizes results of studies of the formation of halogenated
organics in chlorinated cooling waters at the Allen, Kingston, and Shawnee Steam
Plants from June through December 1979. The data indicate that low levels (gener-
ally <20 ppb) of some halogenated organic compounds are formed during power
plant chlorination. The chlorine dosage appears to be directly related to the level
of the halogenated organics identified in the condenser cooling water system. There
is no clearcut pattern that definitely supports any particular relationship between
precursors (e.g. ,amino acid) and halogenated organic compounds. Precursors show
consistent measurements above the detection limit of the analysis techniques. Bro-
mide, ammonia, color, and fulvic acid concentrations at the Allen Plant were
clearly higher than those at the other two plants. The average humic acid concen-
tration was similar at all plants. A temporal trend was also apparent. The amino
acid data showed consistent measurement below the detection limit of the analysis
techniques. The data displayed no apparent temporal trends and no obvious tendency
toward one class or structural type of amino acid.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Croup
Pollution
Halogen Organic
Compounds
Electric Power
Plants
Cooling Water
Chlorination
Amino Acids
Bromides
Ammonia
Color
Humic Acids
Pollution Control
Stationary Sources
Halogenated Oreranics
Fulvic Acid
13B
07C
10 B
13A
07B
06A
20F
08D
IS. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispast)
Unclassified
22. PRICE
EPA Form 2220-1 (1-73)
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Office of Research and Development
Center for Environmental Research Information
Cincinnati, Ohio 45268
OFFICIAL BUSINESS
PENALTY FOR PRIVATE USE, S3OO
AN EQUAL OPPORTUNITY EMPLOYER
POSTAGE AND FEES PAID
US ENVIRONMENTAL PROTECTION AGENCY
EPA-335
PS OOyOJ2V
u i>
H'«'(.
i'3u S
GO II, 6u60i1-
Publication No. EPA-600/7-81-094
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