United States
                    Environmental Protection
                    Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
                    Research and Development
EPA/600/S2-87/016 June 1987
AEPA          Project Summary

                    Water  Quality
                     Characterization  of  an
                     Eastern  Coal  Slurry
                    C. David Cooper
                      Current and projected uses of coal
                    have resulted in several proposals for
                    coal slurry pipelines in the eastern part
                    of the United States.  While several re-
                    searchers have  reported on the water
                    quality aspects of western coal slurries,
                    less work has been done with respect
                    to eastern coals. An experimental study
                    was conducted at the University of Cen-
                    tral Florida from 1982 to 1983 with slur-
                    ries of 50 percent eastern Kentucky coal
                    and 50 percent water. Experiments
                    were conducted with and without the
                    addition of a  corrosion  inhibitor.
                    Twenty-nine water quality parameters
                    were measured as a function of pump-
                    ing time in a 12-meter (40-ft) long, 2.54
                    cm (1 inch) diameter  pipeline con-
                    structed for this study.  Also, the
                    treatability of the 10-day slurry filtrate
                    was assessed using both lime and alum
                    addition.
                      By about the fourth day in the
                    pipeline, most parameters had reached
                    equilibrium values. As expected for this
                    high-ash, medium-sulfur coal,  sulfates,
                    TDS, and conductivity in the slurry fil-
                    trate started high and increased with
                    time. Dissolved oxygen quickly
                    dropped to  near zero. Concentrations
                    of several heavy metals were substan-
                    tial, but organics were  generally very
                    low, about 5-10 mg/L. Trihalomethane
                    formation potential  was quite low,
                    never exceeding 35 ppb. Although the
                    samples were consistent in any one
                    run, samples from different runs on the
                    "same'" coal were significantly differ-
                    ent. Addition of the corrosion inhibitor
                    increased the concentrations of sul-
                    fates, TDS, and  several  other  parame-
                    ters. The characterization of this partic-
                    ular coal  slurry was compared with
those of several western coal slurries
reported in the literature.
  This Project  Summary was devel-
oped by ERA's Hazardous Waste Engi-
neering  Research Laboratory, Cincin-
nati, OH, to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).

Introduction
  The United States is heavily depend-
ent on coal for electricity generation.
This reliance on coal is projected to in-
crease even more in the  future, as oil
and gas decrease in supply and increase
in price. The use of coal is expected to
increase substantially in Florida  and
other southeastern  and Gulf-coast
states, based on their projected popula-
tion growth and on their previously high
percentage use of oil and gas for power
generation.
  In  recent years, the  coal slurry
pipeline has been  promoted as a safe,
reliable, and economical alternative to
railroad  transportation of coal. Basi-
cally, coal slurry pipelining is a means
of transporting coal that involves mix-
ing pulverized coal with water and
pumping it in a steel pipeline as shown
schematically in Figure 1.  First, the coal
is pulverized to a  powder consistency,
then mixed with  an equal weight of
water to form  a slurry. (A 50 percent
coal slurry  is a  pumpable fluid that is
somewhat  more dense and substan-
tially more viscous than water.)  The
slurry is then pumped through a
pipeline, using a number of strategically
placed pumping stations, from the coal
source area to the receiving power

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                                                    Slurry
                                                  Preparation
   Export
Figure 1.
                                                       Power Plant
                              Dewatering Plant
Schematic diagram of a full scale coal slurry pipeline system.
Source: A.D. Dorr is. 1981. Used by permission.
plants. At the receiving sites, the slurry
is dewatered and the coal is burned. The
water is treated before  re-use or dis-
charge.
  One objection to coal slurry pipelines
has  been the possible pollution of
waters at the receiving location by con-
taminants  leached from  the coal while
in the pipeline. Both inorganic and or-
ganic chemicals are solubilized in con-
centrations that depend on the physical
and chemical nature of coal, the water
source, and the time in the pipeline.
Several researchers have studied vari-
ous western coals,  but  less work has
been done with respect to eastern coal
slurries. Eastern coals typically contain
more sulfur than western  coals,  and
they typically have  lower percentages
of the alkaline metals (Na, K, Ca, Mg) in
their ash. Thus, there could be substan-
tial differences between the slurry water
resulting from eastern coals and  that
from western coals.

Purpose and Scope
  The  primary objective of this  work
was to characterize the slurry water re-
sulting from an eastern coal. For charac-
terization, 29 water quality parameters
were  measured on slurry filtrate sam-
pled at various pumping times in a
small pipe-loop system  built for this
study. The parameters included 11 gen-
eral items (such as pH, dissolved solids,
and sulfates); three  organic tests (total
                           organic carbon, trihalomethane forma-
                           tion potential, and phenols); and 15
                           metals. The characteristics observed in
                           this study were then compared with
                           those of other coal slurries reported pre-
                           viously in the literature.
                             Another major objective was to as-
                           sess the effects of the addition of a com-
                           mercial corrosion inhibitor on water
                           quality. Due to the potential for corro-
                           sion of the pipeline by coal slurries,
                           some consideration has been given to
                           adding a  chemical corrosion  inhibitor.
                           The effects of the addition of a nitrite-
                           based inhibitor on slurry water quality
                           were investigated in this research.
                             A third  objective was to address the
                           question  of treatability of the slurry
                           water. Previous researchers have indi-
                           cated that conventional technology is
                            adequate to treat coal slurry waste-
                            waters. Two of the more common treat-
                            ment processes were used to treat the
                            10-day slurry water: high  pH lime pre-
                            cipitation and alum  coagulation. After
                            treatment, the wastewaters were ana-
                            lyzed for the same parameters as above.
                            In addition, the sludges from the treat-
                            ment  processes were subjected to the
                            EP toxicity (leaching) test and tested for
                            eight toxic metals.

                            Experimental Procedures
                              The coal used in this study was ob-
                            tained with the help of personnel at the
                            Mclntosh Power Plant in Lakeland, Flor-
ida. Coal, shipped by unit train from an
eastern Kentucky mine, was received al
that power plant and processed through
the usual sequence of processing steps.
A portion of the feed stream of pulver-
ized coal to one of the burners was di-
verted into a custom designed barrel
that caught the coal  dust, but allowed
the air to exhaust through an attached
filter bag. Approximately two days were
required to obtain a full drum (125 kg),
thus  allowing  for some "time-
averaging" of the coal sample. About 70
percent of the pulverized coal passed a
200 mesh  screen.
  All slurries were processed in a pilot-
scale  system constructed specifically
for this project. A 50-percent solids
slurry was made by adding tap water
from the University of Central Florida's
potable water system to the pulverized
coal in an open top 210-liter steel drum.
The final volume of slurry was mixed in
about one hour by hand-held steel rods
and a small (12  volt, 15  amp)  boat
trolling motor.
  The slurry was  transferred by hand
into a closed top, nitrogen-inerted, 265-
liter steel tank into which was mounted
a Hazleton submersible slurry  pump.
The pump was belt driven with a 1.12
kw motor  and had a speed  controller.
The pump worked very well; because it
was submersible, seal leaks were not a
problem.  A second electric trolling
motor installed in the tank kept the
slurry well mixed during the run. The
slurry was pumped through a 15 meter
long,  2.54 cm diameter schedule 80
steel pipe loop that returned to the bot-
tom of the tank. The pump speed was
adjusted to achieve a slurry velocity of
1.2 to 1.8 m/s in the pipe. The tank was
kept nitrogen-blanketed throughout the
10-day slurry  runs. Cooling  water
flowed through an external  concentric
pipe to maintain the slurry temperature
between 26°C and  32°C for all runs. A
schematic diagram of the experimental
system is presented in Figure 2.
  Samples of the slurry were taken sev-
eral times throughout each 10-day run,
more frequently in the first few days.
The sample times were 3 hours,
7 hours, and 1, 2, 4, 7, and 10 days.
Whole slurry samples were immedi-
ately tested for pH, dissolved oxygen,
and  redox potential. The remaining
samples were  then vacuum filtered
through a 24-cm diameter Whatman
No. 1 filter paper,  and then through a
0.45 micron glass filter. Some of the fil-
trate was then acidified and refrigerated

-------
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 Figure 2.    Schematic diagram of pilot-scale pipe loop used for coal slurry experiments.
for later metals analysis; the rest of the
filtrate was tested for a variety of water
quality parameters.
  All  analytical tests  were conducted
according to Standard Methods for Ex-
amination of  Water and Wastewater,
14th edition (1975), or Methods for the
Analysis of Water and Waste, EPA 6007
4-79-020 (1979). Metals were analyzed
with a DC arc  plasma emissions spec-
trophotometer in lieu  of an atomic ab-
sorption unit. In all, the tests included 11
general water quality parameters, 3
measures of organic content including
trihalomethane formation potential
(THMFP), and 15 metals. All parameters
were  observed on each sample except
for  phenols and THMFP due  to the
lengthy test procedures for these two.
  On  the tenth day,  large volume sam-
ples were drawn for treatability testing.
A laboratory procedure  was used to
simulate conventional treatment proc-
esses that might be anticipated in prac-
tice: coal  separation by sedimentation
and decantation, chemical addition, co-
agulation, flocculation, sedimentation,
and filtration. The chemicals  added
were either lime or alum. The optimum
dose was defined as that which maxi-
mized turbidity removal on small
aliquots of the untreated decantate. The
remainder of the decantate was then
treated at the optimum dose. The final
treated effluent was analyzed for all the
original parameters (except phenols) to
determine removal efficiencies. Finally,
the sludges produced by the treatments
were  later tested  according to  the EP
toxicity test to assess their potential as a
hazardous waste.
   Results and Discussion
     The coal used in this research project
   came by unit train  from eastern  Ken-
   tucky and can be characterized  as  a
   medium sulfur (1.9%), high ash (16%),
   eastern bituminous coal. Some test
   data for the coal used in the four exper-
   imental runs are presented in Tables 1
   and 2. Also, a mineral analysis for the
   major components  in the ignited ash
   showed approximately 50 percent sil-
   ica, 25 percent alumina, 17 percent fer-
   ric  oxide, and about 6 percent  basic
   metal oxides.
     The source water was University of
    Central Florida tap water. The  water
    originated from an  underground  lime-
    stone aquifer and was aerated and chlo-
    rinated prior to distribution to the
    potable water system. Typical source
    water characteristics are shown  along
    with the slurry filtrate analyses.
     Four valid experimental runs were
   completed. Runs 2 and 3 without a com-
   mercial corrosion inhibitor (nitrite
   based) and  Runs  4  and 5 with the in-
   hibitor. (Run 1 was used for equipment
   and procedures shakedown.) The  fact
   that there were significant variations in
   the coal quality was reflected in the re-
   sulting slurry qualities. In all runs, simi-
    lar trends in the  time behavior of the
   slurry contaminants were observed.
    However, in Run 2 the concentrations of
   all  pollutants were  significantly higher
   than in Run 3. A similar situation existed
   for Runs 4 and 5. The slurry with the
   corrosion inhibitor had significantly
    higher concentrations of sulfates, TDS,
   conductivity, and  alkalinity. Differences
in the other parameters were not so pro-
nounced or may have been masked by
differences in the coal samples.
  Results of all the tests are tabulated in
Tables 3 and 4, which present averaged
data of the two runs without the corro-
sion inhibitor and the two with the in-
hibitor. Generally, most parameters
reached equilibrium values in the first
few days of the run. For the runs with-
out inhibitor, the slurry pH dropped im-
mediately on mixing but then rose  to
about 6 by the tenth day for all runs. The
initial pH drop was suppressed by the
corrosion  inhibitor. Dissolved oxygen
quickly dropped to near zero as it re-
acted with the sulfur and other minerals
in the coal.
  As expected for this coal, sulfates
were high and reflected the sulfur con-
tent of the coal. Equilibrium concentra-
tions averaged about 1300 mg/L for the
two runs without corrosion inhibitor,
but surprisingly averaged about 3500
mg/L with the inhibitor. Apparently, the
inhibitor enhanced some ion exchange
process with the coal minerals because
the inhibitor itself did not contain sulfur.
This difference in the sulfates'  behavior
is shown graphically in Figure 3. Figure
4 presents the averaged data for pH,
and highlights the differences observed
with and  without the corrosion in-
hibitor. Furthermore, for the slurry with
the inhibitor, it was observed that coal-
water separation was more difficult.
  The  concentrations  of dissolved or-
ganics were low for this coal slurry, as
indicated by the tests for total organic
carbon and phenols.  TOC was in the
5-10 mg/L range and phenols  were
around 1 ppb. Also, for this particular
coal slurry, THMFP was quite low, never
exceeding 35 ppb. As shown in Tables 3
and 4, the concentrations of several
metals increased one to three orders of
magnitude over the levels in the mix
water,  the largest percentage gainers
being  iron and manganese. Some
heavy  metals exhibited little or no in-
crease.
  Treatability results  are not tabulated
in this Summary. However, it was
shown that both lime and alum  addi-
tions were effective in removing certain
contaminants. Lime treatment  removed
metals better than alum, but  alum re-
moved organics better than  lime. It
should be obvious that the treatment
processing sequence specified at a coal
slurry  receiving site depends on the
characteristics of the particular coal
slurry and the degree of treatment de-

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Table 1. Coal Proximate Analysis (Dry Basis)*

Parameter
%Ash
% Volatiles
% Fixed Carbon
Heating Value (Btu/lb)
% Sulfur
% Passing 200 mesh

Run 2
15.28
32.85
51.87
11,632
2.26
80

Run 3
14.39
36.79
48.82
12,830
1.69
—

Run 4
15.37
36.49
47.63
11,922
1.93
68

Run 5
18.50
35.13
46.37
11,500
1.70
72

Avg.
15.89
35.32
48.67
11,971
1.90
73
Composite as
received, 2
unit trains
(May and
June, 1983)**
14.43
36.10
49.48
12,688
2.13
—
 'SOURCE: Mclntosh Power Plant Chem. Lab., Department ofElec. and Water Utilities, Lake-
          land, Florida
**SOURCE: Mclntosh Power Plant files
Table 2.    Trace Metals Analysis of Coal

                               ppm in ignited ash, as the element
Component
Hg
Se
Cd
Zn
As
Mn
Cu
Pb
Ni
Cr
Ba
Mg
Ag
Run 2
56
92
3.5
106
156
163
221
122
90
231
585
8,490
4.0
Run 3
47
83
4.3
311
238
541
139
101
136
133
837
15,900
2.0
Run 4
63
72
4.2
228
379
408
154
109
133
150
797
8,190
7.0
Run 5
59
63
4.2
219
421
505
110
104
135
123
720
9,610
2.5
Average
56
78
4.1
216
298
404
156
109
124
159
735
10,550
3.9
sired. However, this and previous stud-
ies  reported in the literature, indicate
that conventional treatment with exist-
ing  technology should be sufficient.

Conclusions and
Recommendations
  Eastern coals typically have  higher
sulfur content and less alkaline ash than
western coals. As expected, the slurry
filtrate obtained in this study of an east-
ern coal  exhibited  higher sulfate con-
centrations and  lower  pH values than
would be expected from a typical west-
ern coal.
  For the particular  coal used  in this
study, very few organics  were leached
into the water. TOC  averaged 5-10 mg/L,
phenols  averaged about 1 ppb and
THMFP never  exceeded 35 ppb. Also,
for  this particular coal, very significant
concentrations of iron  (100-500 mg/L)
and manganese (5-25 mg/L) leached
into the water. Concentrations of lead,
nickel, and  aluminum also increased
significantly, but each remained in the
0.1 to 1  mg/L range. It was shown that
oxygen  reacts readily with sulfur and
other minerals in coal slurries, and thus
care should be taken to exclude oxygen
as much as possible when forming,
pumping, or loading coal slurries com-
mercially.
  Coal-water interactions require some
time to  reach  equilibrium. For several
parameters, at least four or five  days
must elapse before equilibrium is ap-
proached. A corrosion inhibitor signifi-
cantly increased the concentrations  of
sulfates, TDS, conductivity, and alkalin-
ity. In addition,  coal-water separation
became more difficult.
  Even though the coal samples used in
this study were from the same source
and were  obtained  in a  "time-
averaged"  manner, the  properties  of
the coal samples were apparently differ-
ent enough to result in significant differ-
ences in the slurry filtrate observed in
"replicate" runs. While the time-behav-
ior trends for most parameters were
similar, absolute levels in the filtrate
were different. Thus, it is recommended
that several replications be conducted
to be able to characterize the slurry of
any particular coal with confidence. In
order to reach valid conclusions about
the behavior of eastern coal slurries, at
least 10 more eastern coals should be
studied.
  Coal slurry wastewaters likely will re-
quire treatment before reuse  or  dis-
charge. Studies thus far indicate  that
present treatment technology can  pro-
vide  adequate treatment, but  the
specific processing scheme will depend
on the particular coal slurry characteris-
tics and site specific regulations.  The
treatment  sludges produced  in  this
study did not fail the EP toxicity test.

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           4OOO
           3000
      I
           2000
           10OO
                                             Runs4 &5(average)
              0
                                             Runs2 &3(average)
                                                        o
                 Mix   01234    56    7    8   9    10
                Water
                                          Time, days
Figure 3.    Effect of corrosion inhibitor (Cl) on sulfates (Runs 2 and 3 without Cl and Runs
            4 and 5 with Cl).

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             7.0
             6.0
        \
             5.0
             4.0
             3.0 I—t
                  Mix   0    1   2    3    4    5    6   7   8    9   10
                 Water
                                           Time, days

Figure 4.    Effect of corrosion inhibitor (Cl) on pH (Runs 2 and 3 without Cl and Runs 4
            and 5 with Cl).
Table 3.    Data Summary Table—Average of Runs 2 and 3
    Parameter, Units
Typical
 Mix
 Water
                                                      Average Concentrations in Slurry Filtrate by Time after Start of Run
3-hours
7-hours
1-day
2-days
4-days
7-days
10-day
General
Sulfates, mg/L                   2           942         1016         1075         1070         1340         1306         1342
Chlorides, mg/L                 19            36           43           58           72           86          108          116
TDS,mg/L                    207          1612         1596         1740         1966         2400         2636         2695
Conductivity, mho/cm          366          1483         1468         1590         1713         1974         2120         2452
Dissolved Oxygen, mg/L          7.9            2.5           0.3           0.2           0.15          0.05          0.05          O.C
Redox Potential, mv            526           211          158           62         -32         -84        -152         -196
pH                             7.0            4.2           4.8           5.2           5.8           5.9           6.2           6.2
Acidity,  mg/L as CaCO3        -96           470          423          480          530          778          878          852
Alkalinity, mg/L as CaCO3       120            12.4          14.3          12.4          22.2          15.2          22.4          13.2
Color, CPU                      6             8            7.5          20.5*         94.5*         69*         132*         280*
Turbidity, JTU                   5.3            3.8          10.9          18.2*         52.2*         67.2*         65.2*         53.5

Organics
TOC, ppm                       6             7.4           5.1           3.6           5.0           6.1           6.2           5.6
THMFP.ppb                    60             —           —           —           —           —           —          23
Phenols, ppb                    —            —           1.0           —           1.0           —           1.2           1.4

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Table 3. (continued)

Parameter, Units
Metals (mg/L)
Hg
Se**
Cd
Zn
As**
Mn
Cu
Al
Fe
Pb
Ni
Cr
Ba
Mg
Ag

Typical
Mix
Water

0.076
0.242
0.006
0.071
0.045
0.009
0.016
0.033
1.28
0.029
0.002
0.004
0.015
11.0
0.002



Average Concentrations in
3-hours

0.21
0.20
0.03
1.29
0.35
4.06
0.21
10.7
58.1
0.30
1.02
0.03
0.16
67
0.02
7-hours

0.18
0.22
0.03
0.96
0.38
4.36
0.01
2.89
92.4
0.30
0.76
0.03
0.12
67
0.02
1-day

0.24
0.21
0.02
0.46
0.36
4.98
0.02
0.78
168
0.30
0.30
0.03
0.09
68
0.01

Slurry Filtrate
2-days

0.26
0.23
0.02
0.20
0.50
6.44
0.02
0.30
214
0.28
0.09
0.02
0.12
67
0.02



by Time after Start of Run
4-days

0.40
0.33
0.03
0.17
0.58
10.2
0.03
0.52
313
0.34
0.10
0.03
0.12
74
0.02
7-days

0.42
0.38
0.04
0.17
0.68
10.5
0.02
0.38
344
0.36
0.08
0.03
0.12
76
0.02
10-days

0.45
0.37
0.04
0.15
0.63
10.9
0.03
0.47
358
0.40
0.14
0.04
0.10
78
0.02
 NOTE:  *=Precipitate formed, data not meaningful.
        **=Data suspect—instrument problems, see quality assurance section.
Table 4.    Data Summary Table—Average of Runs 4 and 5
Parameter, Units
General
Sulfates, mg/L
Chlorides, mg/L
TDS, mg/L
Conductivity, mho/cm
Dissolved Oxygen, mg/L
Redox Potential, mv
pH
Acidity, mg/L as CaCOj
Alkalinity, mg/L as CaCO3
Color, CPU
Turbidity, JTU
Organics
TOC, ppm
THMFP, ppb
Phenols, ppb
Metals (mg/L)
Hg
Se**
Cd
Zn
As"*
Mn
Cu
Al
Fe
Pb
Ni
Cr
Ba
Mg
Ag
Typical
Mix
Water

2
19
207
366
7.9
526
7.0
-96
120
6
5.3

6
60
—

0.076
0.242
0.006
0.071
0.045
0.009
0.016
0.033
1.28
0.029
0.002
0.004
0.015
11.0
0.002
Average Concentrations in
3-hours

1865
66
4398
4630
0.55
141
6.1
402
258
8
3

2.0
—
—

0.05
0.24
0.007
0.09
0.23
7.55
0.07
0.28
0.52
0.36
0.36
0.79
0.06
775
0.008
7-hours

1920
80
4277
4480
0.35
62
6.6
416
208
9
4

3.8
—
—

0.05
0.23
0.006
0.09
0.24
4.80
0.03
0.29
0.45
0.34
0.08
0.03
0.09
108
0.002
1-day

1955
112
4192
4455
0.10
-118
6.8
323
158
8
32*

12.6
—
—

0.054
0.26
0.007
0.07
0.23
3.11
0.03
0.32
11.3
0.32
0.06
0.03
0.08
104
0.007
Slurry Filtrate by Time after Start of Run
2-days

2860
134
4364
4962
0.05
-102
6.3
568
78
7
50*

5.2
—
—

0.09
0.37
0.07
0.76
0.36
8.80
0.03
0.29
737
0.39
0.72
0.04
0.78
728
0.07
4-days

3425
147
5624
5445
0.05
-744
6.2
920
40
8
774*

7.3
—
7.0

0.74
0.37
0.008
0.75
0.36
77.9
0.02
0.34
259
0.39
0.77
0.03
0.75
758
0.075
7-days

3430
160
5920
5410
0.05
-137
6.2
1010
54
8
94*

7.6
—
7.5

0.75
0.33
0.07
0.76
0.40
74.7
0.07
0.46
270
0.40
0.22
0.03
0.09
762
0.078
10-days

3680
178
5712
5362
0.05
-136
6.3
855
58
6
96*

18.6
8
1.0

0.75
0.37
0.07
0.75
0.38
76.6
0.02
0.45
270
0.42
0.32
0.03
0.03
763
0.076
NOTE:
*=Precipitate formed, data not meaningful.
**=Data suspect—instrument problems, see quality assurance section.

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      C. D. Cooper, J.  D. Dietz,  M. J.  Flint, and M. R. Todd are with College of
        Engineering, University of Central florrda, Orlando, Florida 32816.
      Eugene F. Harris is the EPA Project Officer (see below).
      The  complete report, entitled "Water Quality Characterization of an Eastern
        Coal Slurry," (Order No. PB 87-169 9757AS; Cost: $18.95, subject to change)
        will be available only from:
              National Technical Information Service
              5285 Port Royal Road
              Springfield, VA22161
              Telephone: 703-487-4650
      The EPA Project Officer can be contacted at:
              Hazardous Waste Engineering Research Laboratory
              U.S. Environmental Protection Agency
              Cincinnati, OH 45268
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Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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