ML19347F012
| ML19347F012 | |
| Person / Time | |
|---|---|
| Site: | Millstone, Arkansas Nuclear, Duane Arnold  |
| Issue date: | 04/30/1981 |
| From: | Bean R, Mann D, Neitzel D Battelle Memorial Institute, PACIFIC NORTHWEST NATION |
| To: | |
| Shared Package | |
| ML19347F007 | List: |
| References | |
| CON-FIN-B-2098-9 NUDOCS 8105150073 | |
| Download: ML19347F012 (14) | |
Text
_..
O QUARTERLY REPORT QUARTERLY PROGRESS REPORT COVERING PERIOD JANUARY 1 THROUGH MARCH 31, 1981 1
BIOCIDE BY-PRODUCTS IN AQUATIC ENVIRONMENTS R. M. Bean D. C. Mann D. A. Neitzel P. R. Reed, NRC Project Manager April 1981 W
Prepared for the U.S. Nuclear Regulatory Commisssion under a Related Services Agreement with the U. S. Department of Energy Contract DE-AC06-76RL0 1830 FIN No. B2098-9 r
Pacific Northwest Laboratory Richland, Washington-99352 8
810 5 lji 0 <3II'b>
.l
.a s.
q QUARTERLY REPORT BIOCIDE BY-PRODUCTS IN AQUATIC ENVIRONMENTS Period Covered January 1 - March 31,1981 Principal Investigator: Roger M. Bean Co-investigators: Dale C. Mann and Duane A. Neit:al IN~RODUCTION This report presents data from samples collected at three nuclear oower sites, consisting of four units: Duane Arnold Eneroy Center (DAEC) in Iowa, Millstone Nuclear Power Station in Connecticut and two units at Arkansas Nuclear Number One in Arkansas. The sampling locations, sampling protocol and analytical procedures were given in previous quarterly reports (April-June, July-September and September-December 1980).
Some of the data presented in this report for DAEC and Millstone were previously reported but are repeated here for comparison to data obtained from Arkansas samples. The data presented in this progress report are preliminary in nature and incomplete; therefore, care should be exercised in use or interpretation until the program is completed and the data are in fi ci form.
PLANT DESCRIPTIONS The functioning of the cooling systems of the power plants can have a profound ef fect on the chlorination chemistry. Water temperature, biocide concentration, length of biocide exposure to the cooling water, and organic and inorganic content of the water affect the by-products formed in cholorination. Table 1 gives a summary of sampling parameters.
DAEC uses a recirculating cooling system with mechanical draft cooling towers. Chicrination takes place once a day at which time the
'~
6 discharg2 is clos;d and plant op; rates in a closed-loop node (makt-up water is added to compensate for evaporation from the cooling towers).
The plant remains in the closed-loop mode until the chlorine residual drops to below 0.1 ppm (often 8 to 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br />). Then the blowdown is started and con-tinues until-the next chlorination perfod.
Discharge samples were taken imediately upon the initiation of bicwdown.
Millstone is a once-through seawater-cooled plant with four condensers.
One condenser is chlorinated at a time to approximately 2 ppm and is diluted four-fold by water from the other three condensers before discharce.
Residence time of the cooling water in the system is approximately 3 to 5 minutes. Sanpling took place during chlorination of Unit 2.
Arkansas Nuclear Number One consists of two units: Unit 1 is a once-
, through cooled system, and Unit 2 is cooled by a recirculating system using a natural draft cooling tower. Unit 1 is chlorinated once a day to approxi-mately 1.5 ppm and the residence time is about 3 to 5 minutes. Unit 2 is chlorinated once a day to about 4 ppm and residence time within the system varies depending on the blowdown rate but is much longer than that of Unit 1.
Sampling for Unit I took place when a positive residual was detected in the discharge. Unit 2 was sampled about 30 minutes after chlorination to allow the cooling water to mix in the recirculating system. A third sample was taken of the combined effluents from Unit 1 and Unit 2 to investigate the effects that the blowdown from Unit 2 had on the discharge from Unit 1.
WATER SAMPLES Hexane Extracts. 2.0 L of treated water was subsampled from the PVF barrels and extracted with 100 ml hexane to obtain an estimate of the total extractable organic halogen. Grab samples (1.0 L) were also taken 2
.~
-6.
at the same locations as the XAD samples and extracted with 50 mL hexane.
These samples were extracted without pH adjustment or addition on Na 503 2
(Table 2).
Volatile Analysis. Samples for volatile analysis were collected at the intake and discharge'of each unit af ter all residual chlorine was destroyed and the pH adjusted to 4.0-4.5.
Sampling and analytical procedures were " Purge-and-Trap" and are oescribed i,n detail in NUREG/CR-1301 (June 1980).
The principal volatiles identified are the four trihalomethanes, at concen-trations of 0.1-3.7 ppb (Table 3).
XAD-2 Extracts. XAD-2 extracts of about 200 L were collected in dupli-cate at the discharge and intake of each unit. The columns were first ex-tracted with Na CO to recover acids and obenols. The base / neutral frac-2 3 tion was removed by 200 nl ethyl ether and methanol was used to strip any remaining organics. The ether fraction was subsampled for haloform analy-sis and Total Organic Halogen (T0X). The quantity of nonhaloform halogen absorbed on the XAD resin was determined by subtracting haloform halogen as determined by electron capture gas chromatography from the T0X as determined by microcculometry (Table 4). The remainder of the ether sample was evaoorated and separated on silica gel into nonpolar, moderately-polar and very polar fractions. All three feactions were analyzed for T0X (Table 5) and were also analyzed by GC/MS in both CI and EI modes. A preliminary search of the GC/MS data for obvious differences between the discharge and intake samples has not revealed any bass-neutral halogenated hydrocarbons.
A detailed search for chlorination artifacts is planned after all samples are prepared.
Phenols were isolated from the Na 00 extract by acetylatinq with 2 3 acetic annhydride and then extracting with hexane. The procedure is de-tailed in NUREG/CR-1301. Ten species of brominated phenols were tentatively 3
.. ~,.
identified at Arkansas Unit 2.' -(Table 6 lists phenols found; very tentative identifications are denoted by a ?). One chlorinated phenol, trichlorophenol, was found at DAEC. No phenols were found in the Millstone samples.
Because the efficiency of the XAD adsorption for phenols is not known (it is suspected to be low) the phenols cannot be quantitated by this method. However, the XAD technique is very good for qualitative analysis, due to the larce sample.
volume extracted. Quantitative analysis of phenols will be accomplished from the electron capture analysis of methylene chloride extracts of 2.0 L bulk water samples acified to pH 2, using the acetylation /derivatization method.
Laboratory studies have shown this method to be greater than 50" efficient in the recov-ery of trichlorophenol from water. Preliminary results from a DAEC discharge sample indicates the concentration of trichlorophenol to be about 0.4 pob; TISSUE ANALYSIS Invertebrate tissue samples were collected at the intake, discharge and in the environmental plume at the Millstone site. Fresh water mollusks could only be located in the discharge canal at DAEC.
The tissues were homo-genized with ethyl acetate /acteone, the extract concentrated and separated on selica gel and analyzed for T0X (Table 7). Haloforms were analyzed in the organic extract prior to concentration. Althouah detection limits were less than 5.0 ppb, no haloforms were detected in any of the samples.
No sessile organisms were found in the Arkansas One discharge plume.
I t
SEDIMENTS-Sediment cores were collected at the intake, dis:harge, and in the environmental plume at all four units. The top 4 cm of each core was analyzed. The results of the '0X analyses are summarized in Table 8.
4
e -
Sediment samples from DAEC and Millstone were analyzed by GC/!1S and the data are being interpreted. The concentrations of halogenated material from DAEC samples increase from intake, to enviramental (river) plume, to
-discharge canal. The levels of halogen found at the intake represent the naturally occurring levels, while the concentrations found in the intake canal result from the frequent exposure of the sediments to the undiluted chlorinated cooling waters. Sediments from the environmental plume contain an intermediate level of organic-extractable halogen.
Results from the Millstone sediments are more complex. The sediment extracts contained excessive levels of sulfur which interfered with the microcculometric analysis for halogen. The intake sediment extract contained more than 4?. sulfur. The other two samples from Millstone have lower but significantly high concentrations of sulfur. After silica qel chromatography, the levels of halogen dropped significantly which would indicate that the interfering sulfur was adsorbed on the silica gel. Though the levels are low, the resulting concentrations of halogen are higher in the discharge canal sediments than in the intake sediments.
The concentrations of halogens found at the Arkansas site are consistent with our expectations. The levels of halogen increase from tae intake to the embayment to the cooling tower basin. Organic carbon ana'yses have not yet been performed on these samples so the concentrations have been normalized l
to sediment dry weight only.
5
~
- c..
o g; TABLE 1. Summary of Sampling Paraneters 1
OAEC MILLSTONE.
ARKANSAS Unit 1 finTt 2 mixed intake discharge intake, discharge intake discharge discharge discharge Chlorine concentration 0.0
>5 0.0 2.0 0.0 1.4 3.9 1.4 level (ppm) t.
< 0.002 0.07
< 0.002 0.035
< 0.002 0.68 0.30 0.58 f
at sampling (ppm) 4 Time interval between g
addition of chlorine 8-12 hrs 3-5 min 3-5 min' 45 min (3) and sampling i
Organic Carbon (ppm) 12 18 1.7 9.0 15.0 l16.8 24.9 21.9 Inorganic Cargon (ppm) 18 4.5 18 13 26.3 24.3 12.9 25.2 Cl-ion (ppm) 18 80 16190 16210 l26 124-760 138 Br ion (ppm)
(<0.2)b
(<l.0)b 57.4 57.6 0.2 0.2 1.0 0.2 Turbidity (JTU's) 90 330 4
4 10 10 4P 10 Temp ( C) 21 26 18 28 13 19 18 21.
pH source 8.0 7.8 8.0 7.9 7.7 8.1 8.1 8.3 after acidification 4.8 4.7 4.4 4.5 4.4 4.0 4.2 4.3
' A) Sample is a combination of Unit I and Unit 2 discharge effluents,
(
each with different residence tines.
(b) Interference by sulfate ion: detection limits are given.
.a TABLE 2.
Total Organic Chlorine by hexane Extraction (ExpressedasgfgequivalentC1/LWater)
Barrel Environmental Subsamples
" Grab" DAEC Intake 0,0,0 0, 0, O l[sli ppm Cl)
Discharge 0.76, 0.64, 0.31 1.02, 0.40, 0.53 Effluent Plume 0, 0.14, 1.01 MILLSTONE Intake 0, 0.18, 0.15 0.48, 0.05, 0.86 (2.0 ppm Cl)
(Diluted 1 to 4 Discharge 1.44, 1.62, 1.65 0.8, 0, 2.4 prior to sampling)
Effluent Plume 0, 0, 0,78 ARKANSAS Intake 0.45, 0.55, 0.69 0, 0, 22.95 l
i (1.4 ppm Cl)
Unit 1 Discharge 0.48, 2.78, 0.36 65.28, 4.8, 0.78 (3.9 ppm Cl)
Unit 2 Discharge 0.97, 0.88, 1.00 11.27, 0.87, 0.92 Mixed Discharge 0.40, 0.36, 0.74 0.60, 2.04, 0.94 Effluent Plume 0.28, 3.20, 0.61 i
e
--_.-_c-
TABLE 3.
Analysis of Intake and Discharge for Haloforms By Purge and Trap method (expressed as g/L water)
CHCl CHBrCl CHBr Cl CHBr 3
2 2
3 DAEC Intake n(a) n n
n Discharge 0.53 + 0.15(b) n n
n MILLSTONE Intake n
n n
n 0.4(b) 3.7 + 0.16(b)
Discharge n
n ARKAN$AS(c)
Intake 0.2, 0.2 n
n n
Unit 1 1.1, 1.1 1.0, 1.0 0.6, 0.6 C.1, 0.1 Discharge Unit 2 O.7, 0.7 0.7, 0.7 0.7, 0.8 0.2, 0.3 Discharge Mixed 2.1, 1.7 1.9, 1.8 1.0, 1.0 0.1, 0.1 Discharge (a) n = not detected. Detection levels were normally < 0.1.
For DAEC and Millstone, detection levels were 0.3 for CHBr2Cl and 0.4 for CHBr3-(b) Average of 4 replicates + S.D.
(c) Trichloroethane and dichToropropene were found in all water samples at 0.2 g/L. Tetrachloroethylene was found in all water samples at levels ranging rom 3.1to2.5gg/L.
TABLE 4.
Haloform and T0X Measurements on XAD Columns (Expressed as ug equivalent C1/L Water)
Nonhaloform Haloforms T0X Halogen MILLSTONE Intake a.
0.1 0.4 0.3 b.
0.2 1.3 1.1 Discharge a.
2.6 3.4 0.8 4
b.
2.8 4.4 1.6 DUANEARN0g Intake a.
0.02 1.0 1.0 b.
0.2 1.0 0.8 Discharge a.
0.3 2.2 1.9 b.
0.1 1.3 1.2 ARKANSAS NUCLEAR ONE Intake 0.01 0.2 0.2 Unit 1 Discharge 1.5 1.8
- 0. 3 Unit 2 Discharge 1.0 2.4
'4 Mixed Discharge 2.7 2.4 i
m m
.t TABLE 5.
Recovery of Halogens from Intake and Discharge (Expressed as g equivalent C1/L water) j Purge and Trap "Nonhaloform(a)
Hexane /
Haloforms Halogen" Hexane Ether Ether 0.55 0.02 0.43 DAEC Intake
> 5 ppm C1 Discharge 0.48 2.66 0.07 2.04 MILLSTONE Intake 0.40 0.04 0.02 0.16 7.0 ppm C1 (Diluted 1 to 4 prior to sampling)
Discharge 1.76 4.37 0.50 0.11 0.22
?
ARKANSAS Intake 0.11 0.01 0.08 0.05 1.4 ppm Cl Unit 1 1.98 1.17
.0.05 0.05 0.14 Discharge 3.9 ppm Cl Unit 2 1.57 0.69 0.04 0.18 0.37 Discharge 1.4 ppm Cl Mixed 3.45 0.45 0.02 0.05 0.08 Discharge (a) "nonhaloform halogen" is the amount remaining in the ether fraction after evaporation and change of solvent. There may be traces of haloform present, especially bromoform, due to its high boiling point.
TABLE 6.
Phenols Found at Fresh Water Locations ID ARKANSAS UNIT DISCHARGE (XAD' COLUMNS)
Dibromophenol
?
Tribromophenol
+
Dichlorobromophenol(2)
+, +
Chlorodibromophenol (2)
+, +
Methyldibromophenol
?
Methyltribromophenol
?
Nitrobromophenol(2)
+,?
Dinitrobromophenol
?
- No phenols found in other streams
. Solvent extracts still to be analysed DUANE ARNOLD DISCHARGE 1
(XAD Columns)-
~
Trichlorophenol 2.9, 1.5 ng/L (Solvent Extract)
Trichlorophenol 400 ng/L 4
4 I
i i
f 1
.s e
o TABLE 7.
T0X' Analysis of Tissue Samples (Expressed in ug equivalent'C1/g tissue)
Total Halooen (prior to silicia gel)
_ Hexane / Ether 100". Ether
-MILLSTONE Intake 11.1 1 5.2 0.49 0.13
_ Discharge Quarry.
11.5 1 5.2 0.42 0.03 Effluent Plume 11.9 1 3.9 0.45 0.05 DAEC Discharge Canal 0.20 Not Detected Haloforms not found in any samples J
9
. g 9
TABLE 8. T0X Analysis of Sediment Samples Stitco Get Practless og equivalent og equivalent og equivalent 01/g og equivalent 51/g pg equivalent 01/g me egulvelent 01/g C1/e Orr Sedtaent C1/e creante Cerben Orr Sedteent Oreanic Cerben Dry Sedleent 6reente Cerben Dunst Annoto (n=3)
Inteke 0.06 1 0.04 3.ll Otscharge Canal 0.29 + 0.11 40.02 Effluent 0.31 + 0.11 28.05 Mittsionf Intate 2.9*,1.68 511.4*
0.01, 0.01 1.79 0.00, 0.04 14.H Ofscharge Guerry 0.7*, 0.3*
82.9*
0.t8. 0.07 12.11,15.23 0.01, 0.06 12.11, 0.14 fffluent(n=3)
Plume 1.03 1 0.57 135.6 SGNSAS(n=3)
Intake 0.01 + 0.01 0.0" 1 0.02 Cooltas Tower Besta 1.51 1 1.01 0.14 + 0.03
~
O tabs 3=ent 0.35 1 0.45 0.0 Q
= wo-reid excess of sulfur fevnd in the estruts.
ll:0 ci"3 5
- 2:==
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l
s-QUARTERLY REPORT QUARTERLY PROGRESS REPORT COVERING PERIOD JANUARY 1 THROUGH MARCH-31, 1981 BIOCIDE BY-PRODUCTS IN AQUATIC ENVIRONMENTS R. M. Bean D. C. Mann D. A. Neitzel P. R. Reed, NRC Project Manager April 1981 Prepared for the U.S. Nuclear Regulatory Commisssion under a Related Services Agreement with the U. S. Department of Energy Contract DE-AC06-76RLO 1830 FIN No. B2098-9 Pacific Northwest Laboratory Richland, Washington 99352
~
QUARTERLY REPORT BIOCIDE BY-PRODUCTS IN AQUATIC ENVIRON?iENTS Period Covered January 1 - March 31,1981 Principal Investigator: Roger M. Bean Co-investigators: Dale C. Mann and Duane A. Neitzel INTRODUCTION This report presents data from samples col:ected at three nuclear oower sites, consisting of four units: Duane Arnold Enercy Center (DAEC) in Iowa, Millstone Nuclear Power Station in Connecticut and two units at Arkansas Nuclear Number One in Arkansas. The sampling locations, sampling protocol and analytical procedures were given in orevious quarterly reports (April-June, July-September and September-December 1980).
Some of the data presented in this report for DAEC and Millstone were previously reported but are repeated here for comparison to data obtained from Arkansas samples. The data presented in this progress report are preliminary in nature and incomplete; therefore, care should be exercised in use or interpretation until the program I
is completed and the data are in final form.
PLANT DESCRIPTIONS The functioning of the cooling systems of the power plants can have a profound effect on the chlorination chemistry. Water temperature, biocide concentration, length of biocide exposure to the cooling water, and organic and inorganic content of the water af fect the by-products fo ed in i
cholorination. Table 1 gives a summary of sampling parameters.
DAEC uses a recirculating cooling system with mechanical draft cooling towers. Chlorination takes place once a day at which time the
discharge is clos;d and plant operates in a closed-loop mode (make-up water is added to compensate for evaporation from the cooling towers). The plant remains in the closed-loop mode until the chlorine residual drops to below 0.1 ppm (cften 8 to 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br />). Then the blowdown is started and con-tinues until the next chlorination period. Discharge samples were tcken immediately upon the initiation of blowdown.
Millstone is a once-through seawater-cooled plant with four condensers.
One condenser is chlorinated at a time to approximately 2 ppm and is diluted four-fold by water from the other three condensers before discharce.
Residence time of the cooling water in the system is approximately 3 to 5 minutes. Sanpling took place during chlorination of Unit 2.
Arkansas Nuclear Number One consists of two units: Unit 1 is a once-through cooled system, and Unit 2 is cooled by a recirculating system using a natural draft cooling tower.
Unit 1 is chlorinated once a day to approxi-mately 1.5 ppm and the residence time is about 3 to 5 minutes. Unit 2 is chlorinated once c day to about 4 ppm and residence time within the system varies depending on the blowdown rate but is much longer than that of Unit 1.
Sampling for Unit 1 took place when a positive residual was detected in the discharge. Unit 2 was sampled about 30 minutes after chlorination to allow the cooling water to mix in the recirculating system. A third sample was taken of the combined effluents from Unit 1 and Unit 2 to investigate the effects that the blowdown from Unit 2 had on the discharge from Unit 1.
WATER SAMPLES Hexane Extracts. 2.0 L of treated water was subsampled from the PVF barrels and extracted with 100 ml hexane to obtain an estimate of the
. l total extractable organic halogen. Grab samples (1.0 L) were also taken 2
at the same locations as the XAD samples and extracted with 50 mL hexane.
These samples were extracted without pH adjustment or addition on* Na 503 2
(Table 2).
Volatile Analysis. Samples for volatile analysis were collected at the intake and discharge of each unit af ter all residual chlorine was destroyed and the pH adjusted to 4.0-4.5.
Sampling and analytical procedures were " Purge-and-Trao" and are described in detail in NUREG/CR-1301 (June 1980).
i The principal volatiles identified are the four trihalomethanes, at concen-trations of 0.1-3.7 ppb (Table 3).
XAD-2 Extracts. XAD-2 extracts of about 200 L were collected in dupli-cate at the discharge and intake of each unit. The columns were first ex-tracted with Na2CO to recover acids and ohenols. The base / neutral frac-3 tion was removed by 200 ni ethyl ether and methanol was used to strip any remaining organics. The ether fraction was subsampled for haloform analy-sis and Total Organic Halogen (T0X). The quantity of nonhaloform halogen absorbed on the XAD resin was determined by subtracting haloform halogen as determined by electron capture gas chromatography from the T0X as determined by microcculemetry (Table 4). The remainder of the ether sample was evaporated and separated on silica gel into nonpolar, moderately-polar and very polar fractions. All three fractions were analyzed for T0X (Table 5) and were also analyzed by GC/MS in both CI and EI modes. A preliminary search of the GC/f1S data for obvious differences between the discharge and intake samples has not revealed any bass-neutral halogenated hydrocarbons.
A detailed search for chlorination artifacts is planned after all samples are prepared.
Phenols were isolated from the Na CO extract by acetylatino with 2 3 acetic annhydride and then extracting with hexane. The procedure is de-tailed in NUREG/CR-1301. Ten species of brominated phenols were tentatively 3
identified at Arkansas Unit 2.
(Table 6 lists phenols found; very tentative identifications are denoted by a ?). One chlorinated phenol, trichlorophenol, was found at DAEC. No phenols were found in the Millstone samples.
Because the efficiency of the XAD adsorption for phenols is not known (it is suspected to be low) the phenols cannot be quantitated by this method. However, the XA0 technique is very good for qualitative analysis, due to the larce sample volume extracted. Quantitative analysis of phenols will be accomplished from the electron capture analysis of methylene chloride extracts of 2.0 L bulk water samples acified to pH 2, using the acetylation /derivatization method. Laboratory studies have shown this method to be greater than 50% efficient in the recov-ery of trichlorophenol from water.
Preliminary results from a DAEC discharge sample indicates the concentration of trichlorophenol to be about 0.4 peb.
TISSUE ANALYSIS Invertebrate tissue samples were collected at the intake, discharge and in the environmental plume at the Millstone site.
Fresh water mollusks could only be located in the discharge canal at DAEC. The tissues were homo-genized with ethyl acetate /acteone, the extract concentrated and separated on selica gel and analyzed for T0X (Table 7). Haloforms were analyzed in the organic extract prior to concentration. Althouah detection limits were less than 5.0 ppb, no haloforms were detected in any of the samples.
No sessile organisms were found in the Arkansas One discharge plume.
l SEDIMENTS Sediment cores were collected at the intake, discharge, and in the environmental plume at all four units. The top 4 cm of each core was j
analyzed. The results of the T0X analyses are summarized in Table 8.
4
Sediment samples from DAEC and Millstone were analyzed by GC/MS and the data are being interpreted. The concentrations of halogenated material from DAEC samples increase from intake, to environmental (river) plume, to discharge canal. The levels of halogen found at the intake represent-the naturally occurring levels, while the concentrations found in the intake canal result from the frequent exposure of the sediments to the undiluted chlorinated cooling waters. Sediments from the environmental plume contain an intermediate level of organic-extractable halogen.
Results from the Millstone sediments are more complex. The s:diment extracts contained excessive levels of sulfur which interfered with the microcculometric analysis for halogen. The intake sediment extract contained more than 4% sulfur. The other two samples from Millstone have
. lower but significantly high concentrations 5f sulfur. After silica cel chromatography, the levels of halogen aropped significantly which would indicate that the interfering sulfur was adsorbed on the silica gel. Though the levels are low, the resulting concentrations of halogen are higher in the discharge canal sediments than in the intake sediments.
The concentrations of halogens found at the Arkansas site are consistent with our expectations. The levels of halogen increase from the intake to the embayment to the cooling tower basin. Organic carbon analyses have not yet been performed on these samples so the concentrations have been nornalized to sediment dry weight only.
5
.a TABLE 1. Summary of Sampling Paraneters DAEC MILLSTONE ARKANSAS UnitIl Unit 2 mixed intake discharge intake discharge intake discharge discharge discharge Chlorine concentration 0.0
>5 0.0 2.0 0.0 1.4 3.9 1.4 level (ppm)
ChlorineResidual(TRO)
< 0. 002 0.07
< 0.002 0.035
< 0.002 0.68 0.30 0.58 at sampling (ppm)
Time interval between addition of chlorine 8-12 hrs 3-5 min 3-5 min 45 min (a) and sampling Organic Carbon (ppm) 12 18 1.7 9.0 15.0 16.8 24.9 21.9 Inorganic Cargon (ppm) 18 4.5 18 13 26.3 24.3 12.9 25.2 Cl ion (ppm) 18 80 16190 16210 126 124 760 138 Brion (ppm)
(<0.2)D
(<l.0)b 57.4 57.6 0.2 0.2 1.0 0.2 Turbidity (JTU's) 90 330 4
4 10 10 48 10 Temp ( C) 21 26 18 28 13 19 10 21 i
pH source 8.0 7.8 8.0 7.9 7.7 8.1 0.1 8.3 after acidification 4.8 4.7 4.4 4.5 4.4 4.0 4.2 4.3 (a) Sample is a combination of Unit I and Unit 2 discharge effluents, each with different residence tines.
(b) Interference by sulfate ion: detection limits are given.
.=
j TABLE 2.
Total Organic Chlorine by Hexane Extraction (Expressedas/fgequivalentC1/LWater)
Barrel Environmental Subsamples "G rab"-
DAEC Intake 0, 0, ' 0 0, 0, 0 11TlIppmCl)
Discharge 0.76, 0.64, 0.31 1.02, 0.40, 0.53 Effluent Plume 0, 0.14, 1.01 MILLSTONE Intake 0, 0.18, 0.15 0.48, 0.05, 0.86 (2.0 ppm Cl)
(Diluted 1 to 4 Discharge 1.44, 1.62, 1.65 0.8, 0, 2.4 prior to sampling) 4 Effluent Plume 0, 0, 0.78 ARKANSAS Intake 0.45, 0.55, 0.69 0, 0, 22.95 (1.4 ppm Cl)
Unit 1 Discharge 0.48, 2.78, 0.36 65.28, 4.8, 0.78 (3.9 ppm Cl)
Unit 2 Discharge 0.97, 0.88, 1.00 11.27, 0.87, 0.92 Mixed Discharge 0.40, 0.36, 0.74 0.60, 2.04, 0.94 Effluent Plume 0.28, 3.20, 0.61 i
4 0
5 I
e
l' TABLE 3.
Analysis of Intake and Discharge for Haloforms By Perge
'~
and Trap method (expressed as g/L water)
CHCl CHBrCl CHBr Cl CHBr 3
2 2
3 DAEC Intake n(a) n n
n Discharge 0.53 1 0.15(b) n n
n MILLSTONE Intake n
n n
n 0.4(b) 3.7 1 0.16(5)
Discharge n
n ARXANSAS(c)
Intake 0.2, 0.2 n
n n
Unit 1 1.1, 1.1 1.0, 1.0 0.6, 0.6 0.1, 0.1 Discharge Unit 2 0.7, 0.7 0.7, 0.7 0.7, 0.8 0.2, 0.3 Discharge l
Mixed 2.1, 1.7 1.9, 1.8 1.0, 1.0 0.1, 0.1 Discharge (a) n = not detected. Detection levels were normally<0.1.
For DAEC and Millstone, detection levels were 0.3 for CHBr2Cl and 0.4 for CHBr3-(b) Average of 4 replicates + S.D.
(c) Trichloroethane and dichToropropene were found in all water samples at 0.2 g/L. Tetrachloroethylene wi.s found in all water samples at levels ranging rom 3.1to2.5gg/L.
b e
5 TABLE 4.
Haloform and T0X Measurements on X O Columns (Expressed as ug equivalent C1/L Water)
Nonhaloform Haloforms T0X Halogen MILLSTONE Intake a.
0.1 0.4 0.3 b.
0.2 1.3 1.1 Discharge a.
2.6 3.4 0.8 b.
2.8 4.4 1.6 i
DUANE ARNOLD Intake i
a.
0.02 1.0 1.0 b.
0.2 1.0 0.8 Discharge a.
0.3 2.2 1.9 b.
0.1 1.3 1.2 ARKANSAS NUCLEAR ONE Intake 0.01 0.2 0.2 Unit 1 Di charge 1.5 1.8 0.3 t
Unit 2 Discharge 1.0 2.4 1.4 Mixed Distnarge 2.7 2.4
_.,,m
4 TABLE 5.
Recovery of Halogens from Intake and Discharge (Expressed as g equivalent C1/L water)
Purge and Trap "Nonhaloform(a)
Hexane / '
Haloforms Halogen" Hexane Ether Ether DAEC Intake 0.55 0.02 0.43 I
> 5 pp C1 0.07 2.04 l
Discharge 0.48 2.66 I
4 MILLSTONE Intake 0.40 0.04 0.02 0.16 2 0 ppm C1 (Diluted I to 4 prior to sampling)
-Discharge 1.76 4.37 0.50 0.11 0.22 i
ARKANSAS Intake 0.11 0.01 0.08 0.05 1
1.4 ppm Cl Unit 1 1.98 1.17 D.05 0.05 0.14 Discharge 3.9 ppm Cl Unit 2 1.57 0.69 0.04 0.18 0.37 Discharge 1.4 ppm Cl Mixed 3.45 0.45 0.02 0.05 0.08 Discharge (a) "nonhaloform halogen" is the amount remaining in the ether fraction after evaporation and change of solvent. There may be traces of haloform present, especially bromoform, due to its high boiling point.
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TABLE 6.
Phenols Found at Fresh Water Locations ID ARKANSAS UNIT 2 DISCHARGE (XAD COLUMNS)
Dibromophenol
?
Tribromophenol
+
Dichlorobromophenol(2)
+, +
3 Chlorodibromophenol (2)
+, +
Methyldibremophenol
?
Methyltribromophenol
?
Nitrobromophenol(2)
+,7 Dinitrobromophenol
?
- No phenols found in other streams
- Solvent extracts still to be analysed DUANE ARNOLD DISCHARGE (XAD. Columns)
Trichlorophenol 2.9, 1.5 ng/L (Solvent Extract)
Trichlorophenol 400 ng/L i
TABLE 7.
T0X Analysis of Tissue Samples (Expressed in ug equivalent C1/g tissue)
Total Halocen (prior to silicia'cel)
Hexane / Ether 100% Ether MILLSTONE Intake 11.1 1 5.2 0.49 0.13 Discharge Quarry 11.5 1 5.2 0.42 0.03 Effluent Plume 11.9 1 3.9 0.45 0.05 DAEC.
0.20 Not Detected Discharge Canal Haloforms not found in any samples 4
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9 TABLE 8. T0X Analysis of Sediment Samples Stitce tel Fractione cut 1 Cut r og equivalent eg equivalent wg equlvelent 01/g og egulvelent Cl/g og equfveleet [1/g og equivalent E1/g C1/n Orr settment C1/e Greante Carboa Dry Sedtseat Dreaate Carten Dry Sediment creante Carten OU4nt M m0LO (n=3)
Intete 0.06 1 4 04 3.15 01scherpe Canal 0.29 1 0.11 40.02 Effluent 0.31 1 0.11 20.05 MILT 5 tong latde 2.9*,1.6*
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0.01, 0.01 1.79 0.fll0, 0.04 14.64 Stscharge Querry 0.7*,0.3*
02.9*
O.09, 0.07 12.11,15.23 0.01, 0.06 12.11, 8.14 Ifflueet (n.3)
Plume 1.03 + 0.57 135.4 AAGh5A5(n=3)
Intde 0.01 1 0.01 0.01 1 0.02 Coeling y
Temer mesta 1.51 + 1.01 0.14
- 0.03 Q
fessment 0.35 1 0.45 0.0 Q
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