ML20032B176
| ML20032B176 | |
| Person / Time | |
|---|---|
| Site: | San Onofre, Diablo Canyon  |
| Issue date: | 10/31/1981 |
| From: | Emerson R, Harrison F LAWRENCE LIVERMORE NATIONAL LABORATORY |
| To: | NRC OFFICE OF NUCLEAR REGULATORY RESEARCH (RES) |
| References | |
| CON-FIN-A-0119, CON-FIN-A-119 NUREG-CR-1090, UCRL-52555, NUDOCS 8111050041 | |
| Download: ML20032B176 (81) | |
Text
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NU R EG/CR-1090 UCRL-52555 m-mm-w ooeman
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Copper ~ Distribution in Abiotic Compartments of Aquatic Ecosystems Near the Diablo Canyon and San Onofre Nuclear Power Stations
- 11. R. Emerson and F L liarrison l'repared for
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NOTICE i
This report was prepared as an account of work sponsored by I
an agency of the United States Government. Neither the United States Government nor any agency thereof, or any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for any third party's use, or the results of such use, of any infomiation, apparatus product or process disclosed in this report, or represents that its use by such third party would not infringe privately owned rights.
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GPO Salec Program Division of Technical Information and Doctrnent Control i
U S. Nuclear Regulatory Commission Washington, D. C. 20555
$4.25 Printed copy price:
and Natic..al Technical Information Service Springfield, Virginia 22161 4
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NUREG/CR-1090 UCR L-52555 RE Copper Distribution in Abiotic Compartments of Aquatic Ecosystems Near the Diablo Canyon and San Oncfre Nuclear Power Stations Manuscript Completed: July 1981 j
Date Published: October 1981 Prepared by R. R. Emerson and F. L. liarrison Lawrence Livermere National Laboratory 7000 East Avenue l
Livermore, CA 94550 Prepared for Division of IIcalth, Siting and Waste Management l
Office of Nuclear Regulatory Research U.S. Nuclear Regulatory Commission Washington, D.C. 20555 NRC FIN No. A0119
ABSTRACT Copper concentrations were measured in samples of seawater, suspended particles, and bedload sediments collected in intake and discharge areas of the San Onofre and Diablo Canyon Nuclear Power Stations. At the San Onofre Power Station, whose cooling system has half copper nickel and half titanium tubing, the copper in the water column during normal operation ranged from 0.8 to 3.3 pg/L (micrograms per liter). At the Diablo Canyon Power Station, whose cooling system has only titanium tubing (except that in an auxiliary system), copper concentrations ranged from 0.6 to 2.3 pg/L. The San Onofre Station has a long operational history. but the Diablo Canyon Station has never generated electricity. Copper concentrations in ef fluent waters at San Onof re were usually somewhat higher than those in control and intake areas.
Five minutes af ter start up of the main circulators at Diablo Canyon, the copper concentration in the ef fluent water was about 28 pg/L, but decreased rapidly and reached normal levels af ter about 3 h.
Average copper concentrations in intact bedload sediments were 4.4 pg/g at San Onofre and 10.4 pg/g at Diablo Canyon. We noted considerable spatial heterogeneity both at the control and discharge areas, and higher copper concentrations in the <l50-um f raction than in intact sediments.
Copper distribution coef ficients (K 's) of suspended particles were d
higher than those of hedload sediments. At San Onofre the average K 's o f d
suspended particles and bedload sediments were 24,000 and 200, respectively, and at Diablo Canyon were 36,000 and 190, respectively.
Stable copper concentrations in the water had little ef fect on K I d
however, K 's are affected by the organic carbon content of the sediment and d
the species and amount of dissolved organic carbon. Organic (arbon concentrations were higher in sediment samples collected at Diablo Canyon than at San Onofre and in the <l50-pm fraction than in intact sediments.
iii
-~__
CONTENTS Abstract iii Foreword xiii Executive Summary.
1 Recommendations.
3 Introduction 5
Copper Distribution 5
Copper Deposition.
5 Biological Availabilie.v c.f Jopper.
7 Research Objectives.
7 Materials and Methods.
7 Site Characteristics 7
San Onof re Nuclear Power Station 7
Diablo Canyon Nuclear Power Station.
8 Sample Collection and Processing 8
Seawater 12 Suspended Particles.
13 Bedload Sediments.
13 Reagents 14 Copper Analyses.
14 Seawater 14 Suspended Particles.
16 Bedload Sediments 16 Organic Carbon Analyses.
17 Distribution Coefficients.
17 Suspended Particles.
17 Bedload Sediments.
18 Copper Sorption and Desorption Reactions 18 Additions of Organic Compounds 19 Stable Copper Concentrations 19 Results and Discussion 20 Water Column 20 Copper Concentrations.
20 Organic Carbon Concentrations..
22 v
Bedload Sedieents.
23 24 Copper Concentratione.
26 Organic Carbon Concentrations.
Sediment Characterization.
27 27 Copper Distribution Coefficients 31 Suspended Particles.
Bedload Sediments.
31 34 Partitioning of Copper Factors Affecting Partitioning 34 Content of Organic Matter in Sediment 38 Dissolved Organic Mat. rial in Water.
39 42 Stable Copper Concentration.
42 Copper Sorption Rates.
43 Suspended Particles.
Bedload Sedicents 45 49 Rate Constants 53 Impact of Copper Releaseo.
54 Conclusions.
54 Water Colurn 55 Suspended Particles.
56 Bedload Sedicents.
57 Bibliography Appendix A.
Procedure for Cleaning Sample Containers.
61 62 Appendix B.
Supplementary Data.
Vi
4 l
LIST OF FIGURES l
1.
Hypothetical model of the partitioning of copper among abiotic i
compartments in aquatic ecosystems.
6 2.
Samples of seawater and bedload sediments were taken from the study area near the San Onofre Nuclear Power Station. The tubing in the cooling system of this power station is made of 50% copper nickel and 50% titanium.
9 4
i I.
3.
Samples of seawater and bedload sediments were taken from the study area near the Diablo Canyon Nuclear Power Station.
The tubing in the cooling system of this station has been j
replaced with titanium tubing, except for a small auxiliary I
system containing copper-nickel tubing.
10 4.
Concentrations of organic carbon and copper in bedload sediments j
collected near the San Onofre Nuclear Power Station do not seem to be related in samples collected on January 9,1978 (ED, and October 18, 1977 (0).
However, results from the collection on July 21, 1977 (6) suggest a positive correlation.
28 3
5.
The organic carbon concentrations in bedload sediments collected t
near the San Onofre Nuclear Power Station increased with decreasing particle size. The equation for the line is y = 0.0752 + 0.0013x, r = 0.541, and t = 2.945 (p < 0.01). The dashed lines represent the 95%-confidence intervals.
30 6.
A positive correlation is seen between copper distribution coefficient and total coppr.r concentration in bedload sediments t
collected near the San Onof re Nuclear Power Station. The equation for the line is y = 1.297 + 0.0159x, r = 0.726, and t = 3.948 (p < 0.01). Tre dashed lines represent the predicted 95%-confidence intervals. Samples were collected on July 21 (A) 4 and October 18 (0) in 1977 und on January 9,1978 (CD........
35 vii
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l 7.
Little correlation is seen between copper distribution coef ficients and organic carbon concentrations in bedload sediments collected near the San Onofre Nuclear Power Station.
I Regression of organic carbon concentration on the copper distribution coef ficient yields r = 0.407.
Samples were collected on July 21 (A) and October 18 (0) in 1977 and on January 9,1978 (O).
36 8.
A correlation between particle size distribution and the copper distribution coef ficient is seen with bedload sediments collected near the San Onofre Nuclear Power Station. The equation for the i
line is y = 88.8 + 59.9x, r = 0.665, and t = 3.88 (p < 0.001).
37 9.
The association of radiolabeled copper with the particulate phase (>0.45 pu) of unfiltered seawater collected f rom the discharge zone of Nuclear Power Stations varied between stations and among seasons:
(a) Diablo Canyon, August 8, 1977; (b) Diablo Canyon, October 11,1977; (c) San Onof re, October 18, 1977; and (d) San Onofre, January 9,1978.
Note the rapid, initial association.
44 10.
The association of radiolabeled copper with the particulate phase (>0.4 5 pm) of a water-sediment suspension is lower in i
the presence (A) than absence (A) of dissolved organic material.
The water (filtered) and bedload sediments (<l50- m fraction) were collected from the discharge zone of the Diablo Canyon Nuclear Power Station on August 11, 1977. The dissolved organic material (yellow stuff) was added at a concentration of 14 mg C/L.
46 11.
The associatio. of radiolabeled copper with the particulate phase (>0.45 pm) of a water-sediment suspension decreases with increasing concentrations of dissolved organic matter (yellow stuf f).
The water (filtered) and bedload sediments (%10 mg/L of <l50 pm f raction) were collected f rom the discharge zone of the San Onof re 47 Nuclear Power Station on January 9, 1978.
viii
I l
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12.
Changes in the association of radiolabeled copper with the particulate phase (>0,45 pm) of a sediment water suspension.
The water (filtered) and bedload sediments (%10 mg/L of the
<l50-pm fraction) were collected from the discharge zone of the San Onofre Nuclear Power Station on January 9, 1978. At the end of 2 h, the sample was diluted twofold by adding an equal volume o f seawater; (a) uv-treated water only, (b) uv-treated water during sorption, uv-treated water and yellow stuf f (YS,1.44 mg C/L) added af ter 2 h, and (c) uv-treated water plus yellow stuf f (1.44 mg C/L) only.
48 13.
The association of radiolabeled copper with the particulate phase
(>0.45 pm) of a clay water suspension. Filtered seawater and clay (4 mg illite /L) were used (A = 500 pg cu/L and A = N1 pg cu/L).
50 14.
The change in in [F /(F - F )] with time for unfiltered s
s t
seawater samples collected at the Diablo Canyon Nuclear Power Station on October 11, 1977. The equation of the line is y = 0.35 + 0.0086x, and r = 0.979.........
52 IX
.___-.7__yg,
.--_,,,,,,y---.
IIST OF TABLES 1.
Numbers and volumes of water samples collected from study sites at the San Onofre and Diablo Canyon Nuclear Power Stations.
11 2.
Copper concentrations in water cellected near the San Onofre Nuclear Power Station.
21 3.
Copper concentrations in water collected near the Diablo Canyon Nuclear Power Station.
22 4.
Concentrations of 9 articles, copper in particles, and organic carbon in particles and solution in water collected near the Diablo Canyon and San Onofre Nualear Pows Stations.
23 3.
Concentrations of copper and organic carbon in bedload sediments (dry weight) collected near the San Onofre Nuclear Power Station.
25 6.
Concentrations of copper and organic carbon in bedload sediments (dry weight) collected near the Diablo Canyon Nuclear Power Station.
26 7.
Percentage distribution of particle types in intact bedload sediments collected in the discharge zone of the San Onofre 29 and Diablo Canyon Nuclear Power Stations.
8.
Percentage distribution of minerals in intact bedload sediments collected in the discharge zone of the San Onofre and Diablo Canyon Nuclear Power Stations.
29 9.
Copper distribution coefficients of particles in water collected near the Diablo Canyon and San Onofre Nuclear 31 Power Stations.
10.
Copper distribution coefficients of bedload sediments collected 32 near the San Onofre Nuclear Power Static, X
i 11.
Copper distribution coef ficient s of bedload sediments collected in the discharge zone of the Diablo Canyon Nuclear Power Station.
33 12.
Effect of the removal of organic material by combustion on the copper distribution coefficients of bedload sediments collected near the San Onofre and Diablo Canyon Nuclear Power Stations.
39 13.
Effect of the destruction of dissolved organic matter by uv oxidation on the copper distribution coef ficients of the
<150 um fraction of bedload sediments collected near the San Onofre and Diablo Canyon Nuclear Power Stations.
41 14.
Effect of organic chelators on copper distribution coefficients of particles collected from the discharge cove of the Diablo Canyon Nuclear Power Station.
41 15.
Ef fect of stable copper concentrations in seawater on copper distribution coef ficients for clay particles (illite, 4 mg/L) 43 16.
Rate constants (k) and half-times (Tl/2) f reactions 64 describing the sorption of Cu to particles suspended in the water column near the San Onofre and Diablo Canyon Nuclear Power Stations.
53 17.
Maximum values of parameters measured in the discharge zone of San Onofre and Diablo Canyon Nuclear Power Stations.
54 XI
FOREWORD This study is part of a larger research project having three purposes:
(1) to study the behavior of potentially toxic substances introduced into surface waters from nuclear power stations, (2) to determine the impact of these substances on representative, economically important aquat.c species, and (3) to develop models to predict the behavior and impact of these discharged substances. The research was initially directed toward investigating the impact of corrosion products from cooling systems, particularly those of copper. Copper is of special interest because of it s toxicity to aquatic organisms. This investigation was funded by the Office of Nuclear Regulatory Research, Division of Safeguards, Fuel Cycle and En <ironmental Research under FY 1976 Nuclear Regulatory Research Order No. 60-76-144.
The authors thank Jack Dawson and David Rice, Jr. for assisting in collecting and handling field samples, David Rice, Jr. and James Alexander for the APDC/MIBK extractions and atomic absorption spectrometric analysis of camples, and Dorothy Bishop for isolating the dissolved, yellow organic substance (ycIlow stuff).
We are indebted also to Brown and Caldwell Consulting Engineers for allowing us to accompany their staf f members on field trips at San Onofre and to use their boat and equipment, for samples collected by their SCUBA divers, and for the field experiences shared by their research staff.
We also thank the staff of the Pacific Gas and Electric Company and the Southern California Edison for their assistance in coordinating the collection of samples and for their advice and background information. Their cooperation and support made this study possible.
xiii
EXECUTIVE
SUMMARY
The fate of copper released from cooling systems at the San Onofre and Diablo Canyon Power Stations was assessed. The station at San Onofre has a long operational history, but that at Diablo Canyon has never genera - !
electricity. Copper concentrations were quantified in the soluble and particulate fractions of influent and effluent waters and in the bedload sediments.
In addition, copper distribution coef ficients (K s) of d
particles suspended in the water column and present in the bedload sediment s were dete rmined. Samples were collected in April, May, July, and October 1977 4
and in January 1978 ct San Onofre and in June, August, and October 1977 at Diablo Canyon.
3 Copper concentrations in waters collected at San Onofre and Diablo Canyon were low; total copper in the water column at San Onofre ranged from 0.8 to 3.3 pg/L and at Diablo Canyon from 0.6 to 2.3 except during start up.
At San Onofre, concentrations were somewhat lower in influent waters than in effluent waters. At Diablo Canyon, copper concentration in ef fluent waters changed rapidly during the October 1977 start up.
The first water samples contained 28 pg Cu/L, but af ter 3.5 h, intake and discharge waters had similar concentrations.
The amounts of copper in the soluble and particulate fractions of the water varied :onsiderably at both pcwer stations. The particulate phase contained f rom <10 to 75% of the total copper. The dry weignt of particles in the water ranged f rom 2.1 to 53.8 mg/L and copper concentrations in the l
(
suspended particles from 3 to 290 pg/g dry weight. Dif ferences in copper partitioning between the soluble and particulate fractions did not seem to be related to concentrations of soluble and particulate organic carbon in the
(
water.
Insuf ficient data are available to establish a pattern in copper partitioning between power stations or among seasons.
Copper concentre,tions in bedload sediments were lower in samples collected near San Onofre than in those near Diablo Canyon Nuclear Power Station; average concentrations in intact bedload s
- ?* * ; at San Onofre and Diablo Canyon were 4.4 and 10.4 pg Cu/g dry weight, respectively.
Considerable heterogeneity was noted at both sites, and the <150-um fraction had higher copper concentrations than intact sediments.
In general, concentrations of organic carbon were higher in samples collected at Diablo Canyon than at San Onofre and in the <l50-pm fraction than in intact sediments.
An indication of the copper-binding potential of particles in the water column and in bedload sediments was obtained by determining the K s by d
radiotracer techniques. The K a of particles suspended in the water column d
were higher than those of bedload sediments. At San Onofre the average K 's d
of suspended particles and bedload sediments were 24,000 and 200, respectively, and at Diablo Canyor were 36,000 and 190, respectively. We established positive correlation betraen K and copper concentration and a d
negative one between K and particle size.
d j
Laboratory experiments were performed to assess f actors af fecting K
- d Our results indicate that copper af finity is af fected by the organic carbon content of the sediments and by the kinds and quantities of dissolved organic carbon in the water. We detected little effect of stable copper concentration in the water on K *d The rate of association of radiolabeled copper with particles was determined in the laboratory. Rapid sorption of Cu to phrticles occurred in water samples collected f rom the water co.umn and in suspensions of the
<150-um f rac tion o f bedload sediment s.
The time required for * % sorption ranged from <0.7 to 2.5 h.
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l RECOMMENDATIONS i
1.
Ef fect s of start-up.
Changes in the concentrations and chemical forms of copper discharged during start up at other power stations must be documented to assess the impac t of continued use of copper nickel alloys I
in cooling systems and to determine the need for countermessures.
2.
Ef fects of chlorination. The physicochemical forms of copper may change a
during chlorination.
Because chlorination results in the degradation of organic matter, it may destroy organic ligands that bind copper and increase the cancentration of labile copper. We must evaluate the forms t
of copper in the: vater during chlorination to determine changes that may result in partitiraing among abiotic compartments and in toxicity to biota.
f 3.
Iapact on kelp-forist ccmdunities. An important resource of open coastal ecosystems is the kelp community. Because kelp beds provide food and shelter for a large number of species, they are important in maintaining the productivity of an ecosystem. We must assess the ef fects of periodic i
chlorination, he'avy metal, leacbates, and elevated temperature regimes on the structure of the forest communities near tFo San Onofre and Diablo Canyon Nuclear Pcwer Stations.
4.
Effect~ of organic matter content in particles. Additional field and laboratory experim.'nts are needed to determine the ef fect of the organic matter, content in bedload sediments and in suspended particles on copper
-partitioning.
5.
Ef fects of titanium tubing in cooling systems.
been replaced by titanium tubing in units at both San Onofre and Diablo I
Canyon' Nuclear Power Stations. We must determine the quantity and fate of titt.nium leached from cooling systems of nuclear power stations and i
assess the toxicity of titanium to marine biota.
6.
Effe'ets of particle size. Sorption of copper is related to particle size. More information is needed on the role of particle size on the K 's of bedload sediments and suspended particles.
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7.
Water qurlity ef fects. Water quality near nuclear power stations may be altered by material released from station maintenance operations or by discharges from adjacent facilities. We require studies on the i
relationships of pH, salinity, dissolved organic matter, and other water quality partaeters to the Cu K 's of bedload sediments and d
suspended particles.
8.
Soluble forms of copper. Additional efforts are needed to iuentify the chemical forms of soluble copper in the water. The data may be used to k
test updated mathematical models designed to predict chemical speciation.
9, Copper sorption Finetic;. The kinetics of copper binding te particles must be investigated farther. For modeling purposes we need better definition of the rate of copper sorption to particles during the first few minutes af ter contact with seawater. Also, we should extend the assumptions on kinetics to include second and higher order reactions.
)
1 4
INTRODUCTION Pollutants that arise f rom the operation of nuclear power stations and that are discharged in coolar;t seawater may have significant impacts on marine ecosystems in the discharge zone.
Biota may be affected by toxic materials that are released f rom condenser systems into the ef fluent water or produced f rom interactions with the normal constituents of seawater. The toxic materials that may be present will depend on the composition of the condenser tubing. Metals currently in use include copper, nickel, chromium, aluminum, titanium, and zric.
Of these metals, copper is of particular concern because it is used commenly in the fabrication of condenser tubes and is toxic to many aquatic organisms.
COPPER DISTRIBUTION An important factor af fecting the distribution and ultimate fate of copper released into marine environments i s its physicochemical form.
Upon discharge, the metal is partitioned among :.he soluble and particulate fractions of the water and the bedload sediments (Fig. 1).
Soluble copper is diluted by the water mass inte which it is released. Copper in particulate forms may ultimately be deposiced to the sediments; the rate of particle settling depends upon particle praperties and the circulation of water in the part icular environment.
COPPER DEPOSITION The deposition of copper-laden particulate material f rom the water column to bedload sediments is highly probable in of fshore regions close to nuclear reactors. When copper builds up in the bedload sediments, it may be mobilized by particle resuspension and dif fusion across the sediment-water interface.
Particle resuspension depends upon their sir.e, compos ttion, and density, the rate of water flow across the surface, and disturbances from locomotion and feeding of biota. Diffusion depends upon the physical, biological, and chemical processes occurring in the sediments. Because the sediment-seawate r interface is in a dynamic state, bottom sediments can serve either as an important source or sink for copper.
5
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Copper source i
Insoluble Sorption by Soluble precipitate particles phase g
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1.
Hypothetical model of the partitioning of copper among abiotic compartments in aquatic ecosystems.
6
BIOLOGICAL AVAILABILITY OF COPPER i
The physicochemical form and the location of copper in the ecosystem determine its availability to the biota. Organisms can absorb soluble copper across respiratory and digestive surfaces, but only filter feeders can ingest copper in the particulate fraction; deposit feeders living in or near the j
bedload sediments can ingest copper that is associated with surface particles on the sea floor.
During normal operation of power stations, exposure of organisms to chronic, low doses of copper can be expected in the discharge zone.
- However, episodic releases of copper may occur during start up of water through condenser systems af ter an enforced shutdown. Such releases occurred at Diablo Canyon, and organisms were exposed to acute, high doses of copper (Warrick et al., 1975).
RESEARCH OBJECTIVES l
This research project was initiated to determine the quantities, distribution, and fate of copper released from copper nickel alloys used in cooling systems in nuclear power stations located near marine environments.
To fulfill this objective we quantified the copper in abiotic compartments, determined the K 's of particulate material, and evaluated factors that d
a f fect copper partitioning among abiotic compartments. These data are needed to assess the ef fects of the use of copper nickel alloys in condenser systems and to establish the need for mitigation procedures.
MATERIALS AND METHODS SITE CHARACTERISTICS San Onofre Nuclear Power Station The San Onofre Power Station is located in southern California between San Clemente and Oceanside. Field samples were collected primarily in the immediate vicinity cf Unit 1, which currently has 50% copper-nickel (90:10) and 50% titanium tubing in its cooling system; half of the copper-nickel tubing was replaced with titanium tubing in 1974.
The seawater is taken in 7
approximately 980 m of f shore at a depth of 8 m (Fig. 2).
The intake conduit is 3.7 m in diameter and is fitted with a velocity cap to reduce the entrapment of marine organisms. Ef fluent water is discharged through a vertical structure approximately 790 m offshore at a depth of 7 m.
The discharge of the surface-oriented thermal fiume results in a bubbling above the offshore discharge (outfall).
Diablo Canyon Nuclear Power Station The Diablo Canyon facility is located about 11 km north of Avila, l
California, and about 18 km south of Morro Bay.
Intake waters were collected from the cove behind the breakwater (Fig. 3).
Effluent water from the cooling system cascades 20 m down a three-step weir into Diablo Cove. The cooling water system of Unit I requires two cooling water pumps that together circulate 3280 m of seawater per minute through the condenser tubes. The copper-nickel condenser tubing (90:10) originally installed in the system was replaced in 1975 with titanium tubing. However, an auxiliary cooling system still has some copper nickel tubing.
S AMPLE COLLECTION AND PROCESSING At San Onof re, samples were always collected from the outfall region. In July, October, and January, samples were collected also from a control rite 6.7 km south of the outfall and from either the station intake or of t hore intake. The numbers and volumes of samples collected varied during field surveys (Table 1).
The station was in normal operation during collection periods (J. Stock, 1978).
Dredging for the conduit lines for the new units (2 and 3) was in j
progress throughout the year near the discharge site. Water samples in January were taken during intense storms along the southern California coast.
l l
At each collection time, the temperature of the water at the outfall varied with depth; surf ace water was about 2 to 3*C warmer than the bottom water. Temperatures at the surf ace ranged from 14 to 22*C depending on the The salinity of the water collected during 1977 averaged season.
33.5 + 0.5
/oo; the pH ranged from 7.7 to 8.1.
8
San Onofre Creek San Mateo Creek Las Flores Creek San Onofre State Beach
-San Onofre Nuclear Power Station b
San Onofre State Beach I
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Barn kelp b San Mateo kelp
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mi 1.5 b 1 km FIG. 2.
Samples of seawater and bedload sediments were taken from the study area near the San Onofre Nuclear Power Station. The tubing in the cooling system of this power station is made of 50% copper nickel and 50% titanium.
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Power station ft l
0 250 500 1000 N
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0 50 100 150 200 250
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Samples of seawater and bedload sediments were taken from the study area near the Diablo Canyon Nuclear Power Station.. The tubing in the cooling system of this station has been replaced with titanium tubing, except for a small auxiliary system containing copper-nickel tubing.
.~.
TABLE 1.
Numbers and volumes of water samples collected from study sites at the San Onofre and Diablo Canyon Nuclear Power Stations.
i Analyses Filtered seawater Unfiltered seawater Collection Total Labile Total Kd Cu Kd date Cu Cu C
sorption San Onofre Nuclear Power Station 4/5/77 Numbera 1
1 1
Volumeb 3.8 7.5 15 5/5/77 Number 1
1 1
Volume 3.8 7.5 15 7/21/77 Number 1
2 2
1 Volume 3.8 7.5 1
15 10/18/77 Number 1
2 2
1 14 3
Volume 3.8 7.5 1
15 1
1 1/9/78 Number 1
3 7
1 14 3
Volume 3.8 7.5 1
15 1
1 Diablo Canyon Nuclear Power Station 6/7/77 Number 1
2 2
1 1
Volume 3.8 7.5 1
15 3.8 8/11/77 Number 1
2 2
1 8
Volume 3.8 7.5 1
15 1
10/11/77 Number 1
1 2
1 15 Volume 3.8 7.5 1
15 1
" Number of samples collected dt ~5ng each field survey.
~
bLiters.
Three field surveys were made at Diablo Canyon (Table 1).
Samples were not collected under normal operating conditions because power production had not begun. However, water was circulated through the condenser system for various test periods before and af ter the change from copper rickel to titanium cooling tubes in 1975.
In October 1977 af ter a 4.5-no shutdown, we collected effluent samples at various tines af ter start up of the cooling water system of Unit 1.
Samples were collected from the ef fluent stream just before its discharge into Diablo Cove.
11
l The temperature of the water during collection ranged from 11.9 to 13.7*C.
Lower temperatures were expected at Diablo Canyon than at San Onofre because the reactor was not operating and temperatures are lower north of Point t
Conception than in the southern California bight. The average salinity was 32.9 2 0.1
/oo and the average pH was 7.8 2 0.1.
Seawater At the San Onofre Nuclear Power Station, seawater samples from the of f shore intake, discharge, and control sites were collected from a boat. We anchored over the point of interest and used a peristaltic pump to obtain seawater at a rate of about 0.5 L/ min f rom approximately 2 m below the surface; at the discharge site, the water was taken from the bubbling area.
At Diablo Canyon, seawater from the intake cove was collected f rom a boat by the same method as at the San Onofre Station. During one sampling period, water was collected of f the end of the dock, which extends into the intake Samples of ef fluent were collected directly f rom the sump pump at the cove.
base of the discharge tunnel; no boat was required.
Water was filtered in situ through 0.4-pm (pore size), 190-mm (diameter)
Nuclepore membrane filters. Before use, the plastic tubing and filter holder were acid-washed and rinsed with double (glass) distilled water (DDW).
Bectase of the dif ficulty of establishing dif ferences in copper concentrations i
stations where the copper concentrations are only a few parts per billion, at extreme care was taken to keep the equipment and samples free from contamination. The containers used to transport samples were cleaned carefully (see Appendix A), and the water was collected directly through an all plastic pumping system into carboys that had been transported in plastic bags.
Care was taken to keep the bottle cap clean and to prevent entry of contaminants into the sampling containers. The bcttles were then sealed immediately, enclosed in plastic bags, and shipped in crushed ice to Lawrence Livermore National Laboratory (LLNL).
Samples were received at LLNL 4 to 10 h a f tc; they were collected. At each sampling station, one sample of tiltered seawater was acidified to pH 1 with hcl to reduce sorption to the walls of the container. These samples were used to determine total copper.
12
e For the analyses of organic carbon, unfiltered seawater samples were collected by a SCUBA diver at a depth of about 2 m in glass bottles that had been previously heated to 450*C.
These samples were stored in ice chests and returned to LLNL where they were filtered through preheated (450*C) glass-fiber filters immediately after arrival.
Unfiltered seawater was collected also to determine the copper K s of d
the suspended particles.
Seawater from each sampling site was pumped directly into polypropylene bottles. The samples were stored on ice for process *ng af ter arrival at LLNL.
Suspended Particles The quantities of suspended particles in the water were measured by the dry weight of the material retained on the 0.4-um filters.
Af ter the water was filtered, the filter holders were purged of water and the filters were removed, sealed in plastic bags, and shipped on ice to LLNL. The volume of water that passed through each filter was recorded.
Bedload Sediments Bedload sediments were collected from both the outfall and control areas at San Onofre and from the discharge cove at Diablo Canyon. During each field survey, sediments were obtained from the designated sampling areas.
In each area, collections were made at each of three sites within a 30-m radius of each other. A SCUBA diver removed approximately 1 kg of sediment from the top 1
6 to 10 cm of the sea floor in water that was from 6-to 9-m deep. The samples were placed directly into polypropylene bottles, stored on ice, and returned to LLNL within 24 h.
One portion of the sediment samples was treated as an intact sample, while another portion was passed through a 150-pm (pore size) Nitex screen to separate the fine grain component. The <l50-um f raction was considered as that component of the bottom sediment that was resuspendable by such disturbances as dredging and winter-storm activity. Sediment samt'es were washed through screens using filtered water f rom the collection area.
The fine sediment f raction and the water used in the screening process were centrifuged at 90,000 g for 20 min.
The water was decanted, and then the fine sediment was mixed well using a porcelain spatula and refrigerated at 4*C.
4 13
Sediment samples that were collected for size and organic carbon analyses were dried at 100*C for 48 h.-
Samples were stored in glass containers until
~
they were shipped to Dr. Kendall Robinson at the University of California, Los o
Angeles, for analysis of particle-sir.e distribution and total carbon and calcium carbonate contents. Size was determined using a settling tube apparatus, because most of the sediment was <64 pm in diameter. Organic material in the sediment was determined on a Leco Carbon Analyzer in uh ch total carbon and CACO are measured and the organic carbon constituent-is 3
calculated by difference.
Mineral composition was determined by x-ray dif f raction by Dr. Alan Colville at California State University, Los Angeles.
REAGENTS J. T. Baker Ultrex grade nitric, perchloric, and hydrochloric acids were used except where indicated. Double (glass) distilled water was passed through a column of Chelex-100 resin before it was used as a solvent for all reagents and standards. All reagents were of analytical grade or higher purity. Only labware made of polypropylene or Teflon was used. Some of the reagents used in the copper analyses required special treatment to lower the copper concentration in the blank sample. Methyl isobutyl ketone (MIBK) was redistilled, and the solutions of ammonium pyrrolidinedithiocarbamate ( AP9C) and diethylammonium diethyldithiocarbamate (DDDC) and the citrate buf fer were extracted with MIBK. To remove copper from the 1% solution of APDC-DDDC, 10 ml MIBK was added to 100 m1 solution, the mixture shaken for 10 min, and the organic phase discarded. The citrate buf fer was extracted three times with MIBK to remove copper; the reagent was added, the mixture shaken for 1 min, and the organic phase discarded each time.
COPPER ANALYSES Seawater Total soluble copper was analyzed by the method of Kinrade and Van Loon (1974). Before analysis all samples were treated to lower the content of dissolved organic matter. A 200 m1 aliquot of filtered seawater in a Teflon 14
container was acidified to pH 1 using concentrated FC1, 0.05 ml of 35%
H0 was added, and the mixture was boiled for at least I h.
After the 22 I
sample cooled to room temperature, DDW was added to obtain the original volume of the sample. Next the sample was buffered with a citrate buf fer, the pH adjusted to 4.8 to 5 with ultrapure NH 0H, 5 ml of 1% APDC-DDDC solution and 4
40 ml MIBK added, and the mixture shaken for 1 min. Aliquots of the MIBK phase were removed and injected directly into the graphite furnace of the Model 303 Perkin-Elmer Atemic Absorption Spectrometer ( AAS). Standards were
. prepared daily in MIBK; 0.01 ml of an appropriate copper standard in 2N HNO3 was added to 10 ml of MIBK.
For blank samples, pure water was treated similarly to seawater samples.
Blank samples contained 0.032 + 0.015 pg Cu, which was subtracted from the amount of copper measured in each sample.
Copper recoveries were determined using known amounts of CuC1 and 2
64 64 Cu.
The fraction of Cu recovered was 0.98 + 0.01 and of Cu it was 0.95 1 0.03.
Another method used to determine copper was differential pulse anodic l
stripping voltammetry (ASV) (Florence and Batley, 1977). With this technique, l
copper is reduced at a potential more positive than the reduction potential (vs Ag/AgCl reference cell) and concentrated onto a mercury electrode. The amalgamated copper is measured by anodically stripping the copper f rom the mercury electrode by applying a potential gradient and measuring the current produced as the system reaches the oxidation potential of copper. The anodic stripping current, i, is proportional to the equilibrium concentration of the kinetically labile metal, i = kc (M" ), where k is an empirical c
constant whose value depends on the electrode geometry and surface area, cell geometry, stirring efficiency in the cell, length of pre-electrolysis, scan rate of the linear stripping potential, and the diffusion coefficient of copper, both in solution and in mercury (Sugai and Healy,1978).
Total ec.pper in seawater was determined using a Princeton Applied Research 3 74 polarographic analyzer with a Hewlett-Packard microprocessor and X-Y recorder. The electrode system consisted of an Ag/AgC1 reference electrode, a
Pt counter electrode, and a hanging mercury-drop working electrode. All measurements were made at room temperature (20 1 2*C).
To determine the copper concentration, either 5 or 10 ml of seawater was added to a polyethylene cup previously washed with nitric acid and rinsed with purified water, acidified with 50 to 150 pL of perchloric acid, and then allowed to 15
i digest for up to 2 h.
The sample was purged with N for 10 min to remove 2
dissolved oxygen, the copper in the sample was allowed to deposit onto the mercury electrode for 6 nin at -0.600 V, and then the copper was stripped f rom the electrode by scanning from -0.600 to 0.000 V at a scan rate of 10 mV/s.
A medium mercury drop size was used, and the sensitivity of the analyzer was set i
at 1-pA full scale. The naturally occurring chloride ions in seawater provided the supporting electrolyte. Copper concentrations were determined from a standard curve obtained by adding known amounts of copper to the seawater sample.
Suspended Particles Copper in the particulate material collected on the Nuclepore filters was analyzed. Both wet and dry weights of the particles were measured; dry weights were corrected for salt content based on the wet weight before drying.
The filters were placed in platinum crucibles for ashing in a muf fle turnace. The temperature of the furnace was raised from 110 to 450*C at a rate of 50*C/h, and the samples were ashed overnight. Each sample was digested with 10 ml of reagent grade concentrated 11C1, 3 ml of reagent grade i
48% HF, and 1 ml of reagent grade 70% HC10. The samples were evaporated to 4
dryness at about 80*C, dissolved in 10 ml of 2N HNO3, and again dried. Al1 i
samples were brought to volume in 2N llNO and analyzed on the AAS.
Copper 3
concentrations were corrected for the amount of copper in blank samples.
Eedload Sediments Total copper in the nediments was determined af ter acid digestion.
Sediments were powdered using a porcelain mortar and pestle, dried overnigh t at 110*C, and cooled in a desiccator. Duplicate samples of sediment of about 0.5 g were then weighed in platinum crucibles and ashed at 450*C overnight as described for suspended particles. Total copper in the sediments was determined by the same acid-digesticn procedure described for tSe suspe nded 1
particles.
16
.=.
j ORGANIC CARBON ANALYSES Seawater was filtered through glass equipment preheated at 450*C before the soluble and particulate fractions were analyzed for organic carbon.
Particulate organic carbon and dissolved organic carbon were analyzed in filters and filtrates, respectively, with an Oceanography International Carbon Analyzer using the standard persulfate oxidation method (Strickland and Parsons, 1962). Gelman Type A/E glass-fiber filters were used.
i DISTRIBUTION COEFFICIENTS Suspended Particles Copper K 's of particles in the unfiltered seawater were determined.
d Each 1-liter bottle containing seawater was spiked with Cu within a few hours af ter arrival at LLNL. The bottles were placed in a water bath at 12 to 14*C and shaken continuously before filtration. The times betweca the addition of the Cu spike and filtration were genere11y as follows:
0, 0.25, 0.5, 0.75, 1, 4, 8, 12, 16, and 24 h.
The entire sample of seawater was filtered through a 0.45-pm Millipore filter. After filtration, the bottle and filtration apparatus were rinsed with 25 ml of 0.1 N hcl to remove sorbed Cu.
Activities of Cu were determined in the unfiltered seawater, in duplicate samples of the filtrate, in the material on the filter, and in the acid wash. Recovery of the added radionuclide was generally >95%.
In preliminary experiments, the sample of seawater was filtered through two membranes. The first membrane contained activity from Cu on particles a nd Cu sorbed on the membrane; the second membrane contained only sorbed 64 Cu.
The difference between the two represents the activity associated with the particles. The quantities sorbed were extremely small compared to those associated with the particles. The use of two filters was therefore 64 discontinued in later samples, and no correction was made for Cu sorbed by the membrane. All samples were counted in a gamma well counter and corrected for baclground counts and decay te Lbe zero time of the experiment.
17
I The K 's were calculated from the data and the following relationship:
d K
f*
V' (1}
d=
(1 - fs)
W fraction of 64Cu on filter, where fs
=
(1 - fs) = fraction of 6ku in filtrate, weight of water (g),
V
=
t dry weight of particles (g).
i W
=
64 Th e K as defined is dimensionless, and greater sorption of Cu to the d
particulate f raction results in higher Kd s.
i Bedload Sediments f
i The K 's of bedload sediments were determined by weighing 0.75 g of d
sediment dirre tly into acid-washed, 6-oz polyethylene bottles and adding 100 64 ml of filtered seawater that was spiked with tracer quantities of Cu.
The bottleo were placed in a water bath at 12 to 14*C and shaken continuously for approximately 24 h.
The samples were processed similatly to those of suspended particles. Duplicate samples were analyzed.
l Copper Sorption and Desorption Reactions The rate of sorption and desorption of copper was determined for particles in the <150 pm fraction of bedload sedime, ts from the San Onofre Nuclear Power Station discharr e zone. Sixteen replicate samples of 0.7 mg of 64 particles were each suspended in 50 ml of Cu-labeled seawater. The rate 64 o f sorption of Cu onto the particles was determined in eight replicates; one sample s.as filtered every 15 min.
To determine the rate of desorption, an equal vol ime (50 ml) of unlabeled seawater was added to each of eight replicate suspensions that had equilibrated for 2 h, and then a sample was filtered every 15 n in.
All samples were shaken continuously in a water bath 12 to 14*C from the beginning of the experiment until the samples were t
at filtered. The samples were processed as described for the determination of K 's of suspended particles.
d 18
' Additions of Organic Compounds To assess the ef fect of organic chelators on copper partitioning, Cu K 's were determined with particulate material from Diablo Canycn that had been resuspended in seawater containing different chelators.
Suspended particles were collected from the water column with a Sharples field ultracentrifuge; seawater was centrifuged at a rate of about 4 L/ min. Bedload sediments from the discharge cove were wet-sieved through a Nitex screen to obtain a <150-pm fraction. This fraction was selected because particles of this size may be resuspended by tidal currents or storm action.
Reagent grade glycine, sodium citrate, and ethylenediaminetetraacetate (EDTA) were obtained commercially. The yellow stuff (humic substance) was extracted from Alameda Creek water, Sunni Regional Park, Sunol, California.
We isolated the dissolved organic material by an ion-exchange technique and purified it by ultrafiltration using an Amicon UM-2 Diaflo Ultrafilter (Milanovich, 1974). This humic material represents dissolved organic substances that are introduced into estuarine and marine waters from run of f from lan3. When we added this material to seawater that had been photo-oxidized by uv treatment to destroy organic matter, it resulted in a distribution of copper in the different molecular weight fractions that could not be distinguished from that of untreated seawater collected from the power station ecosystem.
Known quantities of particles from the water column and bedload sediments 64 were added to 100 ml of the seawater containing the chelators and Cu.
We u sed 10' M glycine, citrate, and EDTA and solutions of yellow stuf f at 2 mg/L. The K 's were determined as described previously.
d 1
l Sts51e Copper Concentrations To assess the ef fect of stable copper concentration on copper partitioning, Cu K 's f clay particles in seawater containing different d
concentrations of copper were determined in duplicate. A suspension of illite i
that had been equilibrated with seawater was added to seawater spiked with 64' t racer quantities of Cu.
The concentration of suspended particles sas about 4 mg/L, and the total volume of seawater in the 6 oz polypropyicne bottle was 100 ml.
The bottles were shaken for approximately 24 h at room temperature and the contents were processed as described previously.
19
- _ -. _., _.- _ _ __,_. _ - _. - _ _. _. - -., _ _ _ _ - _ ~
RESULTS AND DISCUSSION WATER COLUMN Copper Concentrations Copper concentrations in seawater that are reported in the literature vary greatly with the site and time of collection. Schmidt (1978) in a review of copper concentrations in the marine environment gives a range of 0.06 to 6.7 pg Cu/L for open ocean areas and states that water collected at near-shore sampling sites is generally higher in copper.
The total amount of copper in waters collected in and near the San unofre Nuclear Power Station was low (Table 2).
Tots 1 copper concentrations were usually higher in the discFarge than in the control and intake sites, but differences were frequently small. The highest concentration, 3.3 pg Cu/L, was measured in January 1978. Our values are in the range of those determined in samples collected from San Onofre in a survey conducted by Brown and Caldwell Consulting Engineers in 1976. They reported values from 1 to 8 pg Cu/L (Brown and Caldwell, 1976).
Seawater samples collected at the Diablo Canyon Nuclear Power Station were low in copper except those obtained in October during start up of water circulating through the condenser system (Table 3).
Although titanium was used to replace the copper-nickel tubing in the main aystem at Diablo Canyon, copper is still used in part of the auxiliary cooling system.
Rapid changes in concentration occurred during the October start up (Table 3).
Circulation was started af ter a 4.5-mo shutdown (J. Doyle, 1978).
The first sample was taken about 5 min af ter start up and contained about 28 pg Cu/L. Copper levels dropped to near-background levels af ter about 3.5 h with similar concentrations present in the intake and discharge waters.
The amounts of copper in the soluble and particulate forms varied considerably at both power stations. At the San Onofre facility, the amounts of copper in the particulate phase varied greatly with time of collection, ranging f rom <10 to 75% of the total copper (these percentages can be calculated from data in Table 2).
At Diablo Canyon, the copper partitioning in uncirculated water also varied with time.
In June and August, the copper was about equally distributed between the soluble and particulate phases; in 20
.u
TABLE 2.
Copper concentrations. in water collected near the San Onofre Nuclear Power Station.*
Copper concentrations, pg/L Soluble Particulate Total Collection date Collection site fraction fraction April 4, 1977 Offshore discharge 1.5 b
May 5, 1977 offshore discharge 0.2 0.6 0.8 July 21, 1977 Control 0.6 Station intake 1.2
<0.1 1.2 Station discharge 1.3
<0.1 1.3 Offshore discharge 0.8 0.5 1.3 October 18, 1977 Control 1
<0.1 1
l Offshore intake 1
<0.1 1
l Offshore discharge 1
<0.1 1
l January 9, 1978 Control 1
0.6 1.6 Offshore intake 1.6 Offshore discharge 1.8 1.5 3.3 8 Values +0.3 pg Cu/L.
bhased on the amount of 64Cu that was recovered.
October, 90% was in the soluble phase (Table 3).
Insufficient data are available to establish a pattern between stations or among seasons. Simila r differences are reported at other locations. Harrison et al. (1980) reviewed the data in the literature on the partitioning of copper between the soluble and particulate fractions and provided information on the chemical forms of copper in the soluble fraction of seawater collected at both sites.
Variations in copper concentrations in the particulate fraction of the water can result from dif ferences in the number of particles per unit volume and from dif ferences in the amount of copper associated with the particles.
Particle load differed greatly with collection time at both sites (Table 4).
The lowest, 2.1 mg/L, was measured at Diablo Canyon in August and the highest, 53.8 mg/L, at San Onofre in January. Copper concentrations in the particles ranged from 3 to 290 pg/g dry weight (Table 4).
Differences did not seem to be related to particle load or to particulate and soluble organic carbon. At 21
J TABLE 3.
Copper concentrations in water collected near the Dir.21o Canyon Nuclear Power Station."
Copper concentration, pg/L Collection Collection Soluble Particulate Total date Pumps site fraction fraction-June 6, 1977 Off 1.0 1.3 2.3 August 11, 1977 Off 0.3 0.3 0.6 b
October 11, 1977 On Intake 1.2
<0.1 1.2 c
Discharge d
(T
+ 5 min) 26.0 1.9 27.9-(T
+ 15 min) 1.7 0.1 1.8 (T
+ 30 min) 1.7 0.1 1.8 (T
+ 60 min) 1.4
<0.1 1.4 (T
+ 210 min) 0.6
<0.1 0.6 aValues +0.3 pg Cu/L.
bSample Eollected from intake cove.
" Samples collected from ef fluent stream.
d Time zero, initiation of water flow through the condenser.
both reactor sites, the variations in the fraction associated with the e
particulete phase resulted from changes in both particle load and in copper concentration in the particles.
Organic Carbon Concentrations The general nature and turnover of organic matter in the water column in marine environments has been the subject of a number of reviews (Siegel,1971; Bada and Lee, 1977; Daumas and Saliot, 1977; Duce and Duursma, 1977; Gagosian and Stuermer, 1977; Handa, 1977; Morris and Eglinton, 1977). Interest in these organic compounds stems from their ef fects on biological, geochemical, and physical processes in marine waters.
Our values on dissolved and particulate organic carbon concentrations in coastal waters are in the range reported by others (Siegel,1971; Menzel, 1974). We found little variation with time in the quantities present (Table 4).
In the particulate fraction, the concentrations ranged from 0.2 to 0.6 mg C/L and in the soluble fraction f rom 1.2 to 2.5 mg C/L.
22
l TABLE 4.
Concen rations of particles, copper in particles, and organic carbon in particles and solution in water collected near the Diablo Canyon and San Onofre Nuclear Power Stations.
Collection Collection Particles, Copper in particles, Organic carbon, mg C/L date site mg dry wt/L pg/g dry wt Soluble Particulate Diablo Canyon 6/6/77 Discharge 4.1 290 1.4 0.2 8/11/77 Discharge 2.1 170 2.0 0.5 10/11/77 Discharge 10.7 4
1.8 0.3 San Onofre 7/21/77 offshore discharge 7.6 70 1.6 0.4 10/18/77 Offshore discharge 20.1 3
1.6 0.6 offshore intake 11.3 13 2.5 0.5 Control 3.0 13 1.4 0.2 1/9/78 Offshore discharge 53.8 27 1.5 0.3 Offshore intake 24.6 1.5 0.3 Control 13.1 45 1.2 0.2 Befort the role of these compounds in altering the chemical form of copper in effluents can be understood, more information is needed on the compound s present (amino acids, sugars, fatty acids, steroids, humic substances, etc.)
and their cycling in the ecosystems.
BEDLOAD SEDIMENTS Numerous studies of marine ecosystems show that many trace metals are concentrated in sedimentary material. Copper concentrations in the water are generally a few parts per billion, but in the sediments they range from a few to several hundred parts per million (Schmidt, 1978).
23
Copper Concentrations 3
Copper concentrations in the bedload sediments collected from both San Onofre and Diablo Canyon Power Stations were low.
Sediment samples collected in the of fshore discharge and control areas near the San Onofre Nuclear Power Station contained total copper concentrations ranging f rom 1.1 to 8.1 pg Cu/g dry weight (Table 5).
Considerable heterogeneity was evident both at the control and discharge areas; coppe? concentration varied markedly among the triplicate samples collected within a 30 m radius of each other. However, the
+
highest concentration, 8.1 pg Cu/g dry weight, is low compared to that in sediments polluted by anthropogenic sources; in industrial areas, copper concentrations in sediments may range from 70 to 3000 pg/g (Schmidt, 1978).
l Brown and Caldwell (1976) reported some higher copper concentrations in bedload sediments at San Onofre than those we found.
In sediments collected i
j at both control and discharge zones on May 10, 1976, they report concentrations of about 40 pg Cu/g. However, samples collected on August 12.
and November 9,1976, were in the same range as those we determined in 1977.
No information is available to explain the high concentrations they found in May.
j Significant differences in copper concentrations in intact sediments with 1
time of collection and in samples collected from the two sites were not apparent. However, copper concentrations were always higher in the
<150-pm fraction than in the intact sediments. This was not unexpected
{
because the increased surf ace area with decreased particle size allows a greater copper sorption. A similar relationship between particle size and metal content was shown by others (De Groot et al., 1971; Oliver, 1974).
Copper concentrations in sediments collected at Diablo Canyon were higher but less variable than those at San Onofre (Table 6).
However, this may not be significant because of the limited data base at Diablo Canyon. C rea te r heterogeneity in concentration may occur at Diablo Canyon when the reactor goes on-line -and the sediments are continuously disrupted c.d sorted by the flow of large volumes of turbulent waters.
1 1
4 24 a
e,m_
TABLE 5.
Concentrations of copper and organic carbon in bedload sediments (dry weight) collected near the San Onofre Nuclear Power Station.
Intact
<150-pm Fraction Collection Collection Copper, Orgar,ic carbon,
- Copper, Organic carbon, date site pg/g cg/g pg/g mg/g 4/4/77 Offshore d i scharge 1.4 1.0 8.5 2.9 Control 4.2 0.7 6.2 1.8 5/5/77 Offshore discharge 4.9 0.8 5.5 0.9 Control 4.4 0.8 7.5 0.8 7/21/77 Offshore discharge 1
4.7 1.3
-a 2
6.2 2.2 3
0.4 b
C 4.0 YC 5.4 1.3 Control 1
1.1 1.0 2
1.7 1.2 3
5.4 1.6 C
3.6 4.9 0.7 Y
2.7 1.3 10/18/77 Offshore 1.4)>
discharge 1
5.0 9.4 1.8 2
5.8 1.2 3
8.0 1.1 E
6.3 1.2 Control 1
6.4 1.2 2
4.9 1.3 9.0 1.8 3
8.1 1.6 i
6.5 1.3 1/9/78 Offshore discharge 1
1.4 0.7 4.2 1.1 2
4.4 1.1 Y
2.9 0.9 Control 1
4.5 0.7 5.1 1.4 2
1.5 1.2 4.4 1.0 3
6.3 1.1 4.9 2.0 Y
3-9 1.0 4.8 1.5
" Not dete rmined.
b Composite of samples collected from dif ferent sites.
C Mean of samples collected from dif ferent sites.
25
TABLE 6.
Concentrations of coppe-and organic carbon in bedload sediments (dry weight) collected near the Diablo Canyon Nuclear Power Station.
Intact
<150 mm Fraction Collection Collection Copper, Organic carbon, Copper, Organic carbon, date site pg/g mg/g pg/g mg/g 6/6/77 Discharge 1
9.3
-a 2
6.6 3
14.1 4
9.3 b
C 10.2 8.1 10.5 51 ye 9.8 8/8/77 Discharge 7.8 8.9 7.8 58 10/11/77 Discharge 1
11.9 10.7 2
10.3 7.5 3
12.6 11.9 16.4 C
12.3 17.4 66 x
11.6 10.0 a Not determined.
b Composite sample.
cMeans of samples collected from different sites.
Organic Carbon Concentrations Organic carbon concentrations in the sediments from both San Onofre and Diablo Canyon were less varied than those of copper (Tables 5 and 6).
In general, carbon concentrations were higher in the <150-pm f raction than in intact sediments and in samples collected at Diablo Canyon than at San Onofre. The lower concentration of organic carbon at San Onofre may have resulted because the fine particles that are rich in organic matter are more easily resuspended by the turbulence generated by the discharge of effluents the outfall and consequently can be carried away from the site by currents.
at Organic carbon concentrations in sediments reported in the literature range from 1 to 35 mg C/g (Jaffe and Walters, 1977). The highest values are found in mud and the lowest in sand. The concentrations we determined in the San Onofre samples were low and in the range typical of sand.
In some ecosystems copper content of the sediments is correlated to that of organic 26
[
I i
i content. Jaffee and Walters (1977) determined the correlation coefficient (r) of 0.922 from the linear regression analysis of copper concentrations and organic carbon contents in sediment.
The copper concentrations in the sediments that we collected do not seem to be related to that of organic carbon (Fig. 4).
The results from the July sampling suggest a positive correlation (r = 0.86), but the limited data base 1
precludes a definite conclusion. The absence of a high correlation between organic and copper content in our samples from San Onofre may be the result of i
their low content of organic matter.
The organic content of the sediments is affected by natural seasonal 1
fluctuations in the environment and by man-made disturbances. The role of organic material in copper partitioning probably depends on the quantity and composition of the organic constituents. Humic substances, a major component 1
of organic material in marine sediments, are estimated to comprise up. to 70%
i of the organic constituents (Nissenbaum and Kaplan, 1972).
Sediment Characterization The particle-size distributions of the intact bedload sediments at the two nuclear power stations were quite similar (Tables 7, B-1, and B-2).
The material was almost entirely sand, but the mineral composition varied greatly (Table 8).
At San Onofre the largest fraction of the material was quartz; at Diablo Canyon it was calcite. The particle size distribution of sediments in the control ano outfall areas at San Onofre was similar (Table B-1).
s
[
The intact and <150-pm fractions of bedload sediments from the outfall
)
and control areas at San Onofre increased in organic carbon with decreasing particle size (Fig. 5 and Tables B-1 and B-3).
The Diablo Canyon sediment s e
showed a similar trend in organic carbon and particle size (Tables B-2 and B-4).
A COPPER DISTRIBUTION COEFFICIENTS Soluble copper released f rom cooling systems into the discharge zone may
^
sorb onto particulate material that is suspended in the water column or may be present in the surface layer of the bedload sediments.
Such reactions alter the potential distribution and biological availability of the copper.
27
i 1
I I
I I
I 8
o o
I I
^
6 t
a u
I E
o c)
D
- 4 I
i c.
2 O
4 July 21,1977 f 2 a
oOctober 18,1977 y
oJanuary 9,1978 F
I I
I I
0 O
0.5 1.0 1.5 2.0 Organic carbon - mg/g dry weight i
FIG. 4.
Concentrations of organic carbon and copper in bedload sediments j
collected near the San Onofre Nuclear Power Station do not seem to be related I
in samples collected on January 9,1978 (D), and October 18, 1977 (0).
However, results from the collection on July 21, 1977.(6) suggest a poaitive correlation.
28
TABLE 7.
Percentage distribution of particle types in intact bedload sediments collected in the discharge zone of the San Or.ofre and Diablo Canyon Naclear Power Stations.
Particle type, %
Power station Gravel Sand Silt Clay a
San Onofre 9.9 90.1 0.0 0.0 b
Diablo Canyon 3.3 96.7 0.0 0.0 a Collected on April 5,1977.
b Collected on June 7, 1977.
TABLE 8.
Percentage distribution of minerals in intact bedload sediments collec.ted in the discharge zone of the San Onofre and Diablo Canyon Nuclear Powe. Stations.
Power station Mineral San Onofre Diablo Canyon Quartz 75 15 Biotite 20 1
Calcite (shells) 1-2 45 Calcite (crystals)
<1 35 Calcite (limestone)
Chlorite 3
1 Amphibole
<1 1
Opaque (magnetite, etc.)
<1 1
Total copper in sediments does not necessarily indicate the quantities of copper that may sorb on to sediments.
Stable copper may be present in the crystalline lattice of the particle; this copper does not easily exchange with added copper and is not related to potential binding sites of copper. A better indication of the copper binding potential is the copper K d
sediment.
29
s ';'
l 1
/,
i 5/
ji
~;
)
t.
2.0 s'
u h
~""
o e 1.5 oo b
O 0
l o
g 1.0 o
a 4
o 8
~~~ ~-
.9 0.5 o
e
/
M l
l uo o
0 1
2 3
4 Particle size -i Phi i
FIG. 5.
The organic cr.rbon concentrations in bedioad sediments collected near the San Onofre Nuclear Power Station increased with decreasing particle size.
The equation for the line is y = 0.0752 + 0.0013x, r = 0.541, and t = 2.945
( p < C.01). The dashed lines represent the 95%-confilence intervals.
30
i t
j,.
L.--
+
m 3
g
?
i
+
3 o(
1,- t Q,
f
['l TusN Jed Particle s.,'s K9'
. t, m
r
+
' 'N
,\\
I Copp{erK'th} suspennf particles weh ybtained by radiolabeling r
t
't h
s-i.s c ~
6 M ~ samples bf unf'Ittred seawat ?r wit The K 's ranged from 11,000 t o u.
d 3
9 ',..440 'O, und varied' with the c\\olle, t' ion site and time (Table 9).
The lowest 4-
't g
'? g
~
'j.
g 7
e ll 5 p fou'nd in samt es col' (cted in January at San Onofre. The storm in s,,
Vi e j '
>'ppr W.(luring the colkretion resulteil in high particle concentrations in the t
'wsc{ (Ta'slef 4) and, in aligobabf.lity, in a suspension of particles of Egreater'gmeant size than those during csimer periods.
s
(
no i
'/
f ( ' C '. _ >;; $
j ',
s
/
e
~,
Md loa L Sedit.ent s
'/, y N
,5 1
>c f q.
-),
k -,7 7 [
Y
[},j
,/.
Bottom sedirent collected f rom joth ipower stations had a low affinity for sediments frN,n.5an Onofre ranged from 50 to 400
-[
['k "\\
d9pper.eThe' s of intact r
, y tJ 3
(
Y.'(Table 10 dnd t. hose at Diablo Canyon from 50,to 510 (Table 11).
Agreement bet @ d fdplicates from the same site was' generally good. However, mean
/
K 's in sampirs collected from dif ferent sites within a 30 m radius differed i
d e,
e d
jx
/..
s distrilution coef ficie' cs of particles in water collected J,7 TABLE'9. Copp n
e 4
N-f par'.the Diablo Sanyon gand San Omfre. Nuclear Power Stations.
~~
9 it
+-
4
\\h
\\
f ]'
Co(($tyio'n Copper distribution Collection si(e.
coefficient d a,t
[
f r,
DiabicCanyoy a
Dischargt 27,000 + 6,000 June 6, 1977N August li,,1977 t )'
Di 36,00034,000
.,n\\pcyrge October 11, 1977a uharge 48,000 + 3,000
' San Onof-e
' July 11, 1977 Offshore discharge 45,000 + 11,300 October 18, 1977 Offshore discharge 16,000 + 1,300 Of f s'.. ore intake 30,000 + 1,900 Control 52,000 + 3,000 b
January 9 1978 Offshore discharge 11,000 + 1,600 Offshore intake 19,000 + 2,600 Control 11,000 + 2,500 aSample collected 3.5 h af ter start up.
b Samples collected during a period of storm activity.
31
I TABLE 10.
Copper distribution coef ficients of bedload sedimer.cs collected near the San Onofre Nuclear Power Station.
Copper distribution coef ficient Collection Collectfan Intact
<150-pm fraction date site Discharge Control Discharge Control April 4, 1977 1
50 270 260 2200 70 280 280 2600 Ya 60 2e0 270 2400 May 5, 1977 1
300 250 310 330 320 290 370 390 x
310 270 340 360 July 21 1977 1
150 70 280 430 3
130 80 300 470 Y
140 80 290 450 b
2 400 150 L
380 290 180 260 400 Y
340 160 260 390 1
-C 270 L
390 170 310 560 410 Y
170 290 560 400 October 18, 1977 1
180 250 1180 550 190 240 940 750 Y
180 240 1000 650 2
250 130 1000 L
250 150 1300 930 Y
2 "^;
140 1100 930 3
250 370 620 610 360 450 580 530 Y
300 410 600 570 January 9, 1978 1
150 260 610 890 60 440 280 2500 Y
110 350 440 1700 2
110 150 340 830 t
70 160 440 1230 Y
90 160 390 1000 3
260 560 290 660 Y
270 610 aMean of duplicates.
b Sample lost.
C Insufficient sample collected.
32
TABLE 11.
Copper distribution coef ficients of bedload sediments collected in the discharge zone of the Diablo Canyon Nuclear Power Station.
Collection Collection Copper distribution coef ficient date site Intact
<150-pm frection June 6, 1977 1
160 790 170 930 in 160 860 2
-b 1,300 1,300 1,300 Y
770 3
820 Y
800 760 4
1,100 Y
930 August 8, 1977 CC 150 5,400 160 5,500 Y
160 5,400 October 11, 1977 1
70 12,000 90 12,000 Y
80 12,000 2
190 7,100 230 8,000 Y
210 7,600 3
550 25,000 570 31,000 Y
560 28,000 t
C 490 34,000 500 36,000 Y
500 35,000 i
aMean of duplicate.
(
b Not determined.
C Composite sample.
33
- __~_
markedly. The heterogeneity in copper concentration noted earlier sas evident also in K 's.
At both sites higher K 's were determined with the d
d
<150-pm fraction than with the intact sediments, but the differences were i
smaller in samples from San Onofre than in those from Diablo Canyon.
Comparison of the data on K 's and copper concentrations indicates a d
correlation between these parameters (Fig. 6).
A similar comparison between K 's and organic carbon shows little correlation (Fig. 7).
However, K 8
d d
of sediments from San Onofre increase with decreasing particle size (Fig. 8 a nd Table B-1).
Partitionir.g of Copper In all the samples collected at both San Onof re and Diablo Canyon, the 64 Cu K 's f suspended particles were higher than those of bedload d
sediments. Also, we found a general increase in K 's with a decreasing d
particle size.
The increase in surface area with a smaller particle size allows sorption of increased amounts of organic matter (Jaf fe and Walters, 1977) and contaminants in the marine environment (Cranston and Buckley, 1972).
Sorption of contaminants is not always proportional to specir'ic surf ace area, but also depends on particle composition as well as the chemical species of the contaminant (Duursma and Cross, 1971). Particle sire is probably the most significant long-term factor in determining the partitioning of copper in the sediments. Whether the higher af finity of copper to suspended particles resulted f rom dif ferences in particle size or composition was not established. No data on copper K s were found in the literature.
d FACTORS AFFECTING PARTI 1IONING Trace metals may asscciate with particles by a number of processes.
Davis and IAckie (1978) describe the following, Adsorption of metal ions at oxide surface sites.
o Ion exchange within clay minerals.
e Binding by organically coatco particulate natter or org,anic colloidal e
material.
Adsorption of a metal ligand.
e 34
i i
1 l
i t
4 a
t l
4 I
I I
I 8
o o
,/
a I
/
0 0
a g6 o
1 m
a o
o i
=
a 0
0 l
2 s ',-
4 u
,/',
8 l
~S 2
,/
O
/
/
I I
I I
0 j
0 100 200 300 400 Copper distribution coef ficient l
)
FIG. 6.
A positive corre'tation is seen between copper distribution coefficient and total copper concentration in bedload sedin:ents collected near the San Onofre Nuclear Power Station. The equation for the line is y = 1.297 + 0.0159x, r = 0.726, and t = 3.948 (p < 0.01).
The dashed lines represent the predicted 95%-confidence intervals. Samples were collected on July 21 (A), and October 18 (0) in 1977 and on January 9,1978 (D).
35
t i
1 2.5 y
5
^
I 2.0
?
e a
a o
g 1.5 E
o O
1 n
o e
o o
o o p 1.0 0
o o
c 0.5 5
I I
I I
0O 100 200 300 400 500 Copper distribution coe'ficient i
FIG. 7.
Little correlation is seen between copper distribution coef ficients and organic carbon concentrations in bedload sediments collected near the San Onofre Nuclear Power 9tation. Regression of organic carbon concentration on the copper distribution coef ficient yields r = 0.407.
Samples were collected on July 21 (6), and October 18 (0) in 1977 and on January 9,1978 (O) 36
1 f
I
)
l l
,h' 400 a
E a**,
s o
O
- G.
o,,*,
O
's o
8 300 i
o o
C o
o
.o o
e i
S 200 O
'C O
M o
O 3
O O
,,. s " #
k100 O
a 8
O I
s/
l l
0 1
2 3
4 Particle sic - x Phi FIG. 8.
A correlation between particle size distribution and the copper distribution coef ficient is seen with bedload sediments collected near the San Onofre Nuclear Fower Station. The equation for the line is y = 88.8 + 59.9x, r = 0.665, and t = 3. 8 8 ( p < 0. 001 ).
37
Because of the possible heterogeneity of binding sites on particles, it is difficult to define precisely the reactions that are occurring. Although the empirical tests that we performed do not differentiate among the reactions occurring, they do provide data useful in assessing the amounts and rates of copper binding to particulate material.
Content of Organic Matter in Sediment To assess ne effect of organic constituents in the sediments on their s of a series of af finity or binding capacity for copper, we determined Kd samples before and af ter combustion at 425*C to remove organic material. This t rea tment reduced the K 's, but not in proportion to the organic centent d
(Table 12).
Comparison of the results on sediments collected in July f rom the discharge and control areas shows that although the organic contents were similar, K 's in samples of sediment f rom the discharge area decreased more d
t han those f rom the control area. These data suggest that factors other than organic material can affect K 's significantly.
d It is known that combustion may cause dehydration and. decomposition of a multitude of constituents. According to Jaf fe and Walters (1977), the weight loss that occurs upon ignition is dominated by two r eocesses.
(1) Oxidation of organic carbon.
4 (2) Dehydrolyzation of one or two clay minerals plus decomposition of calcite and dolomite.
At the temperatures of combustion that we used, the first reaction would dominate (llallberg, 1974).
Other studies show that removing organic constituents by hydrogen peroxide treatment can increase particle sorption of copper, fatty acids, hydrocarbons, and phosphate (Meyers and Quinn, 1973a, 1974; Burns and Solomon, 1968).
Meyers and Quinn (1973b) showed that af ter hydrogen peroxide treatment, the sorption capacity decreased if particles were recoated with humic-lipid material extracted from the sediment.
The ef fect of organic matter on the binding of metal ions does not seem to be simple. Evidence is available that indicates that removal of organic matter both increases and decreases K s.
Also, some invest Qators found a d
correlation between metal and organic content of sediments (see discussion above on organic carbon in sediments). Metal ions may be bound to sites on 38
TABLE 12.
Effect of the removal of organic material by combustion on the copper distribution coef ficients of bedload sediments collected near the San Onofre and Diablo Canyon Nuclear Power Stations.
Collection Collection Organic carbon Copper distribution coef ficient date site Fraction mg/g Control Combustion Decrease, %
San Onofre April 5, 1977 Control Intact 0.7 170 80 53
<150-pm 1.8 1500 130 91 Di scha rge Intact 1.0 39 46 0
<150-pm 2.9 230 190 17 July 21, 1977 Control Intact 1.3 280 170 39
<150-pm 420 260 38 Di scha rge Intact 1.3 280 240 14
<150-um 320 280 13 Diablo Canyon August 11, 1977 Discharge Intact 9.0 150 250 0
< l 50-pm 58.0 5400 2000 63 the organic coatings of inorganic particles or on organic particles (organic detritus formed from the degradation of biota).
In some types of sediment, organic carbon may be present primarily as organic coatings. Removal of organic carbon by combustion or hydrogen peroxide treatment of these types of sediment may result in a net increase of binding sites because of exposure af additional inorganic sites; an increase of K w uld be then expected.
If, d
however, sediment contains both organic coatings and detritus, more binding sites may he provided by organic detritus than coatings, and the removal of organic carbon would result in a net decrease in the number of binding sites and a decrease in K
- d Dissolved Organic Material in Water The presence of organic matter in the water as well as on the particles may af fect K 's.
The concentrations of dissolved organic material in d
seawater vary greatly with the ecosystem.
Low concentrations are typical of 39
open ocean and some :npolluted coastal ecosystems; high concentrations are typical of productive estuaries and waters receiving anthropogenic wastes such as municipal treatment plant ef fluents.
The effect of dissolved organic material in seawater on the K
's of d
copper was assessed using the <150-pm fraction of bedload sediments from both power station sites.
In one series or experiments, K 's of copper were -
d determined using untreated, filtered seawater and some that was subjected to uv oxidation to destroy organic matter.
Significantly higher K
'8
""I' d
obtained in the uv-treated water (Table 13).
The addition of organic chelators to filterad seawater collected from the Diablo Canyon discharge zone yielded a range of effects on copper partitioning (Table 14). The K 's were determined using the <l50-pm f raction of d
bottom sediments and suspended particles centrifuged f rom the water column.
The presence of the hexadentate ligand EDTA, which forms the most stable copper ccmplexes of the compounds listed, had little ef fect on the Kd*
bedload sediments, but resulted in significantly lower values for suspended particles. Citratc, a tridentate ligand that is a natural metabolite, had little effect )n the K f suspended particles but resulted in higher values d
for bedload sedim nts; glycine, a bidentate ligand that is an essential amino acid, resulted in higher values for both. The effect of yellow stuf f was determined only with suspended particles. Yellow stuff, or Gelbstoff, is a humic substance consisting of polymeric molecules having large numbers of 4
hydrogen bonds, aromatic cores, and functional groups that can bind cations.
Addition of yellow stuf f resulted in a lower K than the control. These d
data indicate that the effect of a chelator depends not only on its copper stability constant, but on the composition of the particles.
Effects of glycine on K 's f zine were evalus.ted by Siegel (1966).
He d
investigated the adsorption of zine glycine complexes to synthetic cation exchangers and various clays. His results indicate that the zinc monoglycinate was sorbed almost as strongly as the divalent zine ion, but the diglycinate (zero-charged species) did not seem to be sorbed at all.
The interactions of organic chelators, metals, and binding sites on particles are of great importance in the fate of metals added to ecosystems.
However, reactions are complex, and insuf ficient data are available currently to understand the behavior completely.
40
l TABLE 13.
Effect of the destruction of dissolved organic matter by uv oxidat ion on the copper distribution coef ficient s of the <l 50-pm f raction of bedload sediments collected near the San Onofre and Diablo Canyon Nuclear Power Stations.
Collection Power Collection Collection distribution coefficient, date station site Control uv oxidation 5/5/77 San Onofre Discharge 170 360 control 180 4,300 6/6/77 Diablo Canyon Discharge 17,000 21,000 8/8/77 Diablo Canyon Discharge 6,200 23,000 TABLE 14.
Effect of organic chelators on copper distribution coef ficients of particles collected from the discharge cove of the Diablo Canyon Nuclear Power Station.
Copper distribution coef ficient
<l 50 pm fraction of Suspended 4
d b
Chelator bedload sediments particles i
None 1,300C 6,300 1,400 7,300 EDTA 1,600 2.200 1,600 2.400 Citrate 19,000 4,800 20,000 5,400 Glycine 20,000 32,000 21,000 20,000 e
4,100 Yellow stuff 2,000
^1x 10-5 M except yellow stuff, which was 2 mg/L.
b Collected by centrifugation f rom the water column with a portable centrifuge.
C Duplicates.
o 41
Additional variables in copper partitioning to be considered include pH, salinity, and temperature. However, within the high-energy environment at San Onof re these parameters did not vary significantly. The importance of pH is minimized by the relatively constant pH of marine waters and the fact that maxinum sorption of copper occurs within a pH range of 7 to 12 (Kester et al.,
i 1975). Stern (1975) also found that copper is rapidly sorbed to particles n
seawater within a broad pH range.
In addition, he found that the sorption of copper did not dif fer at 4 and 20*C and in the light and dark.
Stable Copper Concentration A preliminary experiment was conducted to determine the importance of stable copper concentration in the water on copper K 's f clay particles.
d Concentrations as high as 1000 pg Cu/L did not significantly change the af finity of copper to illite particles (Table 15).
These data indicate that the K f partic' es having a given composition may not change significantly d
e ven though the apper concentrations in the water may vary with time and location.
Kester et al. (1975), who studied the fractica of copper sorbed to illite, hydrous ferrous oxide, beach sand, and polyethylene surfaces, reported similar results. They found that the solid substrates were f ar f rom saturated at the concentrations tested and that the equilibrium was reached within 24 to 30 h.
The data from our experiments and in the literature indicate that at the range of copper concentrations and pH's found in power station ef fluents, K s of d
particles would be expected to be independent of stable copper concentrations.
COPPER SORPTION RATES The final distribution of the copper released will depend not only on whether it sorbs to particles, but on where in the ecosystem the reaction If the sorption is relatively rapid, it will result in a higher occurs.
en increased sorption o f concentration of copper in the suspended particles, copper to the bedload sediments, and a greater potential for buildup of copper in the iamediate vicinity of the station.
42
e TABLE 15.
Effect of stable copper concentrations in seawater on copper distribution coef ficient s for clay particles (illite, 4 mg/L).
Copper addition Copper distribution coef ficient 3
pg/L 24 h 36 h h
None 8,100 8,100 8,600 7,700 50 7,900 7,500 8,200 6,000 500 7,300 7,600 7,600 6,500 1000 7,300 6,700 8,900 7,800 a Equilibration t ime.
hCopper concentration in seawater was 1 to 2 pg/L.
Suspended Particles The association of radiolabeled copper with particles was determined in the laboratory in water samples collected
- from the water column both at Diablo Canyon and San Onofre Nuclear Power Stations. The percentage of Cu in the particulate fraction increased with time until steady state conditions were i
approached (Fig. 9).
A significant percentage of the added Cu was already associated with the particles in water samples filtered immediately after spiking (filtration time about 10 min). This rapid association was lowest 1
(about 1% of the total 16% sorbed) in the sample from Diablo Canyon collected on August 11, 1977, and was highest (17% of the total 64% sorbed) in the sample from San Onofre collected on January 9, 1978.
In the absence of data on the amount of Cu associated with the particles at time zero, the results might be interpreted to indicate: (1) the presence of a class of binding sites on the particles for which the inital recction phase i s poorly resolved by this method or (2) the presence of two types of binding sites, one that has a half-time of sorption that is less than 10 min (Compartment I) and one that equilibrates more slowly and has a time constant measurable by the method (Compartment II).
43
15 8,
b I
I I
I i
i A
A A
A 10 4
4 5
I 50 I
I I
I I
I O
a e
50 I
I I
I d
I I
I I
c 0 30 3
40 3-A A
20 /4 30 4
~
20 10 10 I
I I
I I
I I
O O
O 5
10 15 20 25 0
5 10 15 20 25 Time - h
. FIG. 9.
The association of radiolabeled copper with the particulate phase
-(>0.45 pm) of unfiltered seawater collected f rom the discharge zone of j
Nuclear Power Stations varied between stations and among seasons:
(a)
Diablo Canyon, August 8, 1977; (b) Diablo Canyon, October 11,1977; (c) San Onofre, October 18, 1977; and (d) San Onofre, January 9, 1978. Note the rapid, initial association.
44
We can see from the data in Fig. 9 that the time required for 50% of the sorption varied with the water sample. The most rapid sorption occurred with the particles in water samples f rom San Onof re collected on October 18, 1978, and the slowest with those from Diablo Canyon taken on August 11, 1978; the t ime required for 50% sorption was <0.2 h and 2.5 h, respectively.
Bedload Sediments 1
The association of radiolabeled copper to the <l50-pm fraction of bedload sediments was determined in the presence and absence of yellow stuf f in the seawatte.
Yellow stuf f at concentrations of 1.4 mg C/L in seawater decreased the amount or Cu associated with the particulate fraction by approximately 40% (Fig. 10).
With increasing amounts of dissolved organic matter in seawater, the amount of radiolabeled copper associated with particles in the <l50 pm f raction of San Onof re bedload sediments decreased until a plateau was reached (Fig. 11).
The amount of copper associated with the particulate phase
~
decreased by about 50% with the addition of yellow stuf f at a concentration of 2 mg C/L.
Increasing soluble organic material had no significant effect on 64Cu partitioning.
Copper released from a point source is diluted in the receiving waters.
Dilution af fects partitioning between the soluble and particulate fractions.
We used samples of the <150-um f raction of bedload sediments f rom San Onofre to determine the effect of dilution and the pcesence of dissolved organic matter on sorption end desorption reactions. The following technique was employed: radiolabeled copper was added to the particulate fraction and the percentage associated with particles was determined during a 2-h period a t 15 min intervals. The sample was diluted twofold, and then the percentage associated during a 2-b desorption period was moaitored. Sorption reactions occurred more rapidly in the presence of yellow stuf f (Fig. 12).
- Hcwever, little desorption occurred either in the presence of yellow stuf f during the sorption period or af ter its addition at the time of dilution.
In the sisence of added yellow stuf f, approximately 50% of the copper associated with the particulate material was desorbed in 2 h af ter dilotion. These data indicate that the quantities of dissolved organic matter in the water can significantly a f fect copper sorption-desorption reactions.
45
16 i
l i
ae 12 I
a a
g 5
c 8 A
o 3
y
^
3 e'
e 4
/
ll I
I I
I 0
O 5
10 15 20 25 Time - h FIG. 10.
The association of radiolabeled copper with the particulate phase
(>0.45 pm) of a water sediment suspension is lower in the presence (6) than absence ( A) of dissolved organic material. The water (filtered) and bedload sediments (<150-um fraction) were collected from the discharge zone of the Diabla Canyon Nuclear Power Station on August 11, 1977. The dissolved organic material (yellow stuf f) was added at a concentration of 1.4 mg C/L.
46
15 i
i i
i i
i 12 24 1 9 t
==
o E6 o
a 2O
?o 3
I I
I 0
O 1.0 2.0 3.0 Soluble organic carbon - mg/l FIC. 11.
The association of radiolabeled copper with the particulate phase
(>0.45 pm) of a water-sedime.nt suspension decreases with increasing concentrations of dissolved organic matter (yellow stuf f).
The water (filtered) and bedload sediments (%10 mg/L of <150-pm fraction) were collected from the discharge zone of the San Onofre Nuclear Power Station on January 9, 1978.
47
20 l
l l
8 I
a Dilutiori 15
- s e s's %
. A A
10
% 'A A
-a -a A
5 i
i l
e i
i i
20 I
I I
I b
A A
A i
~ ^
^
15
'T "ilution + YS D
^
g I 10 t
_~"
5 g
- Sorption A Desorption M
i l
l i
l l
i 20 g i
i i
eDilution
/
15
_g _,_, m_ y _
10 5
i l
i l
i l
i i
1 2
3 4
Time - h FIC. 12.
Changes in the association of radiolabeled copper with the particulate phase (>0.45 pm) of a sediment-water suspension. The wate r (filtered) and bedload sediments (%10 mg/L of the <l50-um fraction) were collected from the discharge zone of the San Onofre Nuclear Power Station on January 9, 197R.
At the end of 2 h, the sample was diluted twofold by adding an equal volume of seawater; (a) uv-treated water only; (b) uv-treated wate r during sorption with uv-t reated water and yellow stuf f (YS, 1.44 eg C/L) added af ter 2 h, c) ov-treated water plus yellow stuf f (1.44 mg C/L) only.
48
The sorption of copper to illite that was f ree of organic matter was deternined also. At concentrations in seawater of approximately 1 and 500 pg Cu/L, the association of radiolabeled copper with the clay was rapid 64 (Fig. 13).
The concentration of Cu in the particulate fraction increased until a steady state of sorption-cesorption was reached.
Rate Constants If the rate-liciting reaction of the sorption of copper to particles can be described mathematically, then models can be used to predict the quantities e
sorbed with time and at various locations in an ecosystem. Let us consider the interaction of copper (Cu) and particles (P):
cup.
(2) 9 Cu +P
=
Because two reactant s are present, we would expect the teaction to follow second order kinetics. However, a reaction may have pseudo first order kinetics if the concentration of one of the reactants is very much greater than that of the other and its change in concentration is negligible compared to the change in concentration of the other reactant.
The integrated form of the rate expression for a first order reaction is
(( _
= In ( A )
I, (3) kt
^ t/
where k = the rate constant, i
the initial concentration of the reactant, and A
=
the concentration of the react qnt at time t.
A
=
Let us designap-the concentration of radiolabeled copper that will react with the particles as A and the concentration available to react at time t 64 as A. A is a to the concentration of Cu (corrected for decay) on the filter at steaoy state conditicn of sorption-desorption (F ); A is a to 64 the concentration of Cu on the filter at steady-state conditions minus that on the filter at any time (F - F ).
Equation (3) may be rearranged to s
t t
n 49
25 g
i i
20 A
g I
t 15 E
^
C 10 o
a 3
P 5'
I I
I I
O O
5 10 15 20 25 Time - h r
FIG. 13.
The association of radiolabeled copper with the particulate phase
(>0.45 pm) of a clay-water suspension.
Filtered seawater and clay (4 mg illite /L) were used (A = 500 pg cu/L, A = %1 pg cu/L).
50
l
/ 7 h
s (4)
Inl
- F )l= kt.
F\\s t
For a pseudo first-order reaction, we can expect that a plot of in [F,/(F, - F ) j vs ti ae will give a straight line having a slope of k.
t Results obtained from the experiment to follow the sorption of Cu t o particles in unfiltered water samples collected from Diablo Canyon ou October 11, 1979, were analyzed to determine if the reaction could be described appropriately by pseudo first order kinetics. A plot of the relationship in [F /F - F vs time gave a straight line (Tig. 14). s s t Data f rom the other experiments to determine sorption rates were treated similarly and the results of the calculations are summarized in Table 16. Half-times of sorption (T]/2 = 0.693/k) ranged from 1.4 to 3.5 h. It seems 64 that the changes we measured in the percentage cf Cu on the filter with t ime can be described by pseudo first order kinetics. However, the values of T calculated from k are different from those determined graphically from 1/2 64 the amount of time elapsed between the addition of the Cu spike and before 50% of the maximum sorption is achieved (see Fig. 9). The dif ferences are related to the percentage of Cu associated with the particles in the sample processed immediately af ter the Cu spike compared to the total 64Cu associated with the particles at steady-state sorption-aesorption (Table 16). The dif ferences are greater in those experiments that showed a large fraction of the Cu associated with the particles initially. Further analyses of th2 data do not seem sarranted. Better definition of rate ] constants awaits use of techniques that permit resolution of the amounts associated with the particles during the first few minutes af ter the Cu spike is added. Our experimental data indicate that copper dischargsd into the environment would be rapidly sorbed to particulate matter. Within the first hour, significant f ractions of the copper would be associated with particles, although organic material on the particles and in the water may alter the rates of sorption. Organic matter was found to slow the r1te and extent of sorption of zine to silica particles in seawater (Willey, 1977). Other studies demonstrated the rapid sorption of copper to particles and, in most cases, equilibrium was approached in about 24 h (Stern, 1975; Kester et al., 1975). Sorption rates also depend on the type of substrate (Bilinski et al., 1976). 51
\\ l I [ l l I I I I 1.5 a-u.- 1.0 LL. ~ 5 0.5 1 I I I I I O 20 40 60 80 100 120 Time - min FIG. 14. The change in in [F /(F - F )) with time for unfiltered j s s t seawater samples collected at the Diablo Canyon Nuclear Power Station on October 11, 1977. The equation of the line is y = 0.35 + 0.0086x, and r = 0.979. 52 ____.--_.--------------_________a
TABLE 16. Late constants (k) and half-times (Tl/2) f reactions describing 64 t he sorption of Cu to particles suspended in the water column near the San Onof re and Diablo Canyon Nuclear Power Stations. Collection Collection Kinetic model analysis Graphical analysis site date k(h~ ) r Tl/2(h) gjy T Sorbed Diablo Canyon 8/8/77 0.2 0.96 3.5 2.5 16 10/11/77 0.5 0.88 1.4 0.5 3.5 San Onofre 10/8/77 0.2 0.48 3.5 0.2 64 1/9/78 0.5 0.99 1.4 0.5 40 Correlation coefficient. bPercent sorbed, 64Cu activity associated with the particles immediately 64 af ter the spike as a percentage of the total Cu activity associated with the particles at steady-state conditions of sorption-desorption. Copper that is sorbed to particles may be desorbed upon dilution of the e f fluent or change in the kinds and quantities of organic material in the water. We found greater desorption of Cu in the absence of dissolved organic matter; in the presence of organic matter, little desorption occurred. Stern (1975) found insignificant amounts of copper were desorbed f rom particles and attributed this to the high af finity of copper to the particles. The amount of desorption from particles would be expected to decrease with time because sites within the coatings and within the crystalline matrix are less accessible (Duursma et al., 1974). IMPACT OF COPPER RELEASES The data acquired f rom our field sampling can be used to assess the extent of impact of copper releases on the ecosystems adjacent to the San Onofre and Diablo Canyon Nuclear Power Stations. Because of the small number of fiald surveys taken, we cannot presume to have described the extremes in concentration that may occur in the ecosystems. However, by examining the maximum values of the parameters measured (Table 17), we can obtain an indication of possible adverse ef fects. 53
TABLE 17. Maximum values of parameters measured in the discharge zone of San Onofre and Diablo Canyon Nuc1 car Power Stations. Parameter San Onofre Diablo Canyon Water Column Copper (pg/L) Total 3 28 A Cua 2 27 Soluble fraction 1.8 26 Pargiculatefractions 1.5 2 DOC (mg C/L) 2 2 Suspended Particles Copper (pg/g dry wt) 70 390 Particle load (mg dry wt/L) 54 11 Distribution coef ficient 50,000 47,000 C POC (mg C/L) 0.6 0.5 Intcet Bedload Sediment. Copper (pg/g dry wt) 8 12 Distribution coefficient 400 600 d 0.2 0.8 TOC Predominant Size Sand Sand Discharge min us intake copper concentration. b Dissolved organic carbon. CParticulate organic carbon. d Total organic carbon. CONCLUSIONS Water Column Copper in the water column at San Onofre was in the range of concentrations typical of environments receiving little or no input from anthropogenic sources (Schmidt, 1978); the maximum concentration found was 3.3 pg/L. Concentrations at Diablo Canyon were in this low range also except during start up of water circulating through the cooling system. At both sites dif ferences in copper concentrations between intake and discharge waters were small; the maximum dif ference measured was 2 pg Cu/L. Because the addition of copper to the water column was small and suf ficient organic ligands were present to complex most of the copper (Harrison et, al., 1980), we 54
can expect little or no impact from the release of copper from San Onofre or Diablo Canyon Power Stations when station operations are normal and no chemicals are added to the circulating waters. Adverse ef fects f rom copper releases into the water column may occur when water circulation is started up again through the condenser systems af ter a shutdown and when the coolant waters are chlorinated to prevent fouling of the condenser tubing. We detected elevated concentrations of copper in the discharge waters during start up at Diablo Canyon. The maximum concentration of 28 pg Cu/L that we found was low compared to the 1800 and 7700 pg Cu/L reported earlier when copper nickel tubing was present in the system (Warrick et al., 1975). We did not condt.c t a field survey at San Onofre during start up. However, all indications are that a pulae of copper would be released here also. Before the impact of such a release can be asssessed, data on the peak concentration of copper, the duration of the pulse, and the physicochemical form of the copper are needed. J Chlorination results in the degradation of organic matter in the water. This practice may affect the biota by changing the chemical form of potentially toxic metals in the discharge waters. Organic ligands that bind copper may be destroyed and the concentrations of labile copper increased. The impact of the destruction of organic matter would be greatest when copper concentrations are at =easonal highs. Suspended Particles Copper concentrations in and K 's of suspended particles, which is the d f raction in the water that is important to filter feeders, were considerably higher than those in intact bedload sediment s (Table 17). liigher K '
- i n d
suspended particles than in bedload sediments probably reflect differences in particle size and composition. However, the quantities of particles in the water are <,enerally low. The highest particle load was observed at San Onofre during a storm. The greatest impact of copper releases on filter feeders would probably occur if copper was discharged when the quantities of particles in the water column were increased by storm or tidal currents to levels that stimulate rather than inhibit the feeding response. 55
Eedload Sediments Bedload sediments collected in the discharge area of both the San Onofre and Diablo Canyon Power Stations were low in copper, and the copper K 's of d the sediments were low. The sediraent from both sites consisted primarily of sand, and little organic matter was present. These results indicate little or i no build up of copper in the sediment at either site and a small potential for build up in the future. s s 56
BIBLIOGRAPHY J. L. Bada and C. Lee, " Decomposition and Alteration of Organic Compounds Dissolved in Seawater," Mar. Chem. 5, 523-534 (1977). H. Bilinski, S. Kozar, and M. Branica, " Adsorption of Heavy Metal Traces on Particulate Matter in Sea Water," J. Colloid Interface Sci. 3 211 (1976). 1 Brown and Caldwell, San Onofre Nuclear Generating Station Unit 1, Environmental Technical Specifications Annual Operating Report, Broun and Caldwell, Environmental Science Division, Pasadena, CA, (1976), Vol. 1. P. A. Burns and M. Solomon, " Phosphate Adsorption by Kaolin in Saline Environments," Proc. Nat. Shellfish Assoc. 59, 121-125 (1968). 1 R. E. Cranston and D. E. Buckley, " Mercury Pathways in a River and Estuary," Environ. Sci. Technol. 6, 274-278 (1972). R. A. Daumas and A. Saliot, "The Inventory in Marine Organic Chemistry," Mar. Chem. 5, 417-426 (1977). J. A. Davis and J. O. Leckie, "Effect of Adsorbed Complexing Ligands on Tr.sce Metal Uptake by Hydrous Oxides," Environ. Sci. Technol. 12, 1309-1315 (1978). A. J. De Groot, J. J. M. De Coeij, and C. Zegers, " Contents and Behavior of Mercury as Compared with Other Heavy Metals in Sediments from the Rivers Rhine and Ems," Geol. Mijnbouw 50, 393-398 (1971). J. Doyle, Pacific Gas and Electric Company, San Ramon, CA, private communication (1978). R. A. Duce and E. K. Duursma, " Input of Organic Matter to the Ocean," Mar. Chem. 5, 319-340 (1977). 57
E. K. Duursma and M. G. Cross " Marine Sediment s and Radioactivity" i n Radioactivity in the Marine Environment (U.S. National Acidemy of Science, Washington, DC, 1971), pp. 147-160. E. K. Duursma, P. Parsi, and C. Statham " Fixation of Radionuclides with Time by Marine sediments", in Activities of the International Laboratory of Marine Radioactivity, Monaco, International Atenic Energy Agency, Vienna, Austria, 163 (1974), pp. 107-116. T.M. Florence and G. E. Batley, " Determination of Copper in Seawater by Ar>dic Stripping Voltammetry," J. Electroanal. Chem. 75, 791-798 (1977). R. B. Gagosian and D.11. Stuermer, "The Cycling of Biogenic Compounds and Their Diagenetically Transformed Products in Seawater," Mar. Chem. 3, 605-632 (1977). R. O. Itallberg, " Metal Distribution Along a Profile of an Inter-Tidal Area," Est. Coast. Mar. Sci. 2, 153-170 (1974). N. Handa, " Land Sources of Marina Organic Matter," Mar. Chem. 5, 341-360 (1977). F. L. Harrison, D. J. Bishop, R. R. Eme son, and D. W. Rice, Jr., Concentration and Speciation of Copper in Receiving Waters of the San Onof re and Diablo Canyon Nuclear Power Stations, Lawrence Livermone National Laboratory, Livermore, CA, UCRL-52706, NUREG/CR-07 50 (1980).
- D. Jaf fe and J. K. Walters, " Intertidal Truce Metal Concentrations in Some
~ Sediment s f rom iluber Estuary," Sci. Total Environ. 7_, 1-15 (1977). D. R. Kester, T. P. O'Connor, and R.ll. Byrne, Jr., " Solution Chemistry, Solubility, and Adsorption Equilibria of Iron, Cobalt and Copper in Marine q Systems," Thalassia Jugos1. y,121-123 (1975). J. D. Kinrade and J. C. Van Loon, " Solvent Extraction for l'se with Flame Atomic Absorption Spectrometry," Anal. Chem, g, 1894-1898 (1974)
- Available for purchase from the NRC/GPO Sales Program, II. S. Nuclear Regulatory Commission, Washington, DC 20555 and/er the Nat.ional Technical Informat ion Service, Springfield, VA 22161.
58
D.W. Menzel, " Primary Productivity, Dissolved and Particulate Organic Matter, and the Sites of Oxidation of Org,nic Matter," in The Sea Edward Coldberg, Ed. ) (John Wiley and Sons, Inc. New York, 1974), Vol. 5, pp. 659-679. P. A. Meyers and J. G. At; inn,. " Factors Af f(cting the Association of Fat t y Acide uith Mineral Particles in Sea Water," Geschim. Cosmochim. Acta 37, 1745-1759 (' 9 73a ). P. A. Meyers and J. C. Quinn, " Association of Hydrocarbon and Mineral Particles in Saline Solution," Nature 244, 23-24 (1973b). P. A. Meyers and J. G. Quinn, "Crganic Matter on Clay Minerals and Marine Sediments--Effect on Adsorption of Dissolved Copper, Phosphate and Lipids from Saline Solutions," Chem. Geol. 13, 63-68 (1974). F. P. Milanovich, Physical, Chemical, and In Vivo Studies of the Naturally Occurring Dissolved Yellow Organic Substances of Fresh Water", Ph.D. thesis, University of Crlifo nia, Davis, CA (1974). R. J. Morris and C. Eglicton, " Fate and Recycling of Carbon Compounds," Mar. Chem. 5, 559-572 (1977). A. Nissenbaum and J. R. Kaplan, " Chemical and Isotopic Evidence for the in Sitt-Origin of Marine Humic Substances," Limmol. Oceance., 17, 570-582 (1972). B. G. Oliver and H. Agemian, "Furthe r Studies on t he Heavy Metal Levels in Ottowa and Rideau River Sediments," in Scientific Series No. 37, Inlana Wate r Eranch, Dept. of Environment, Ottowa, Canada (1974). R. L. Schmidt, " Copper in the Marine Environment - Part 1", CRC Critical Rev. Environ. Control 8, 101-152 (1978). A. Siegel, " Equilibrium Binding Studies of Zinc-Glycine Complexes to Ion Er. change Resins and Clays," Geochim. Cosmochim. Acta 30, 757-758 (1966). 59
A. Siegel, " Metal-Organic Interactions in the Marine Environment," in Organic Compound s in Aquatic Environment, S.J. Faust and J.V. Hunter, Eds. (Marcel ( Dekker, New Brunswick, NJ, 1971) pp. 265-295. D. Stern, "A Laboratory Investigation of Trace Metal Adsorption on a Marine Sediment," Ph.D. thesis, University of New Hampshire, Durham, NH (1975). J. Stock, Southern California Edison Company, Rosemead, CA, private communication (1978). J. D. H. Strickland and T. R. Parsons, A Practical Handbook of Seawater Analysis, (Finneries Research Board of Canada, Ottowa, Canada, 1962). S. F. Sugai and M. L. Healy, "Voltammetric Studies of the Organic Association of Copper and Lead in Two Canadian Inlets," Mar. Chem. 6, 291-308 (1978). J. W. Warrick, S. Sharp, and S. J. Friedrick, Chemical, Biological, and Corrosion Investigations Related to the Testing of the Diablo Canyon Unit Cooling Water System, Pacific Gas and Electric, Department of Engineering, San Ramon, CA 7333-129-75 (1975). I l i J. D. Willey, " Coprecipitation of Zine with Silica in Seawater and in Distilled Water," Mar. Chem. 5, 267-290 (1977). l JAS/js u0 _., ~
i APPENDIX
A. PROCEDURE
FOR CLEANING SAMPLE CONTAINERS ) CONTAINERS OF <10 pg Cu/L SAMPLES New polypropylene containers were filled with reagent grade, concentrated ~ t HNO and stored at room temperature for at least 7 d to leach out metal 3 c ontaminant s. The acid was then removed, and the containers rinsed five times with double (glass) distilled water (DDW) and filled with 0.05% Ultrex HNO in DDW. Af ter at least 4 d, the dilute acid was discarded and the 3 containers were rinsed five times with DDW and then stored filled with DDW until use. CONTAINERS OF >10 pg Cu/L SAMPLES New polypropylene containers were soaked for at least 2 d in a 2% MICRO bath. The containers were removed from the bath, rinsed fiva times with DDW, drained, and stored in sealed plastic bags until use. 61
APPENDIX B. SUPPLEMENTARY DATA TABLE B-1. Percentage distri' ution of size f ractions in bedload sediments collected I near the St.a Onofre Nuclear P iwer Station. Gravel Sand Silt Clay Date Site Intact <150 pm Intact <150 pm Intact <150 pm Intact <l50 pm 4/77 Discharge 1 9.89 0 90.11 71.16 0 28.84 0 0 Control 1 1.52 0 98.48 72.63 0 27.37 0 0 5/77 Discharge 1 0 0 9 6. 8:. 95.2f 3.16 4.74 0 0 Control 1 0.97 0 99.03 75.60 0 24.40 0 0 7/77 Discharge 1 0 10.59 0 89.41 13.21 0 2 0 86.79 3 7.77 97.23 0 0 0 Control 1 1.68 98.32 0 91.66 8.34 0 2 0 26.60 0 3 0 73.40 t 1 10/77 Discharge 1 6.56 87.47 5.71 0.26 I I 0.63 2 17.21( 0 79.01 [ 76.55 3.58( 22.83 0.20 [ 3 0 I 91.05 8.66 0.29 1 Control 1 0 86.02 13.72 0.26 j i i 1 2 1.44 0 95.16 { 69.31 3.25 (30.40 0.09p 0.28 3 0 61.98 1 37.43 l 0.59 1/78 Discharge 1 4.84 0 94.79 94.53 0.31 5.33 0.05 0.15 2 1.12 0 97.86 56.35 0.96 43.04 0.06 0.61 3 15.73 0.18 Control 1 6.11 77.93 2 4.89 0 87.74 61.71 7.23 37.61 0.14 0.68 3 0 0 58.75 67.33 40.81 31.97 0.45 0.71
- Not determined.
62
TABLE B-2. Percentage distribution of size fractions in bedload sediments collected near the Diablo Canyon Nuclear Power Station. \\ ) Date Site ravel Sand Silt Clay ) Intact <l50 pm Intact <l50 pm Intact <l50 pm Intact <l50 pm 6/77 Discharge
- 1 3.32 96.68 0
0 8/77 Discharge 1 0.74 99.26 0 0 10/77 Discharge 1 1.25 1 88.40 10.35 1 0 1 0 90.20 L,61.23 6.79l 38.75 O 0l 2 3.01 \\ 3 0.90 84.24 14.86I O i i I acomposite of four samples. b No analycis. 63
TABLE B-3. Percentage of organic carbon and calcium carbonate in bedload sediments collected near the San Onofre Power Station. c Date Site Organic carbon Inorganic carbon Total carbon Calcium carbonate Y intact <150 pm Intact <150 pm Intact <150 pm Intact <150 pm 4/77 Discharge 1 0.10 0.29 0.58 0.10 0.68 0.39 4.80 0.80 Control 1 0.07 0.18 0.21 0.02 0.28 0.20 1.73 0.16 5/77 Discharge 1 0.08 0.09 0.29 0.06 0.37 0.15 2.40 0.40 Control 1 0.08 0.08 0.49 0.11 0.57 0.19 4.05 0.90 7/77 Discharge 1 0.13 0.30 0.43 2.52 2 0.22 0.05 0.27 0.45 3 0.04 0.94 0.98 7.80 2.52 Control 1 0.10 0.30 0.40 ? 0.12 0.24 0.36 1.985 0.08 3 0.16 0.01 0.17 10/77 Discharge 1 0.14 1 0.57 0.71 1 4.75 I l i 0.20 O.21 5.50 0.03 0.79 2 0.12l 0.18 0.66l I I 3 0.11 1 0.04 0.15 t 0.30 i Control 1 0.11 1 0.17 0.29 l 1.45 1 1 i l i 2 0.13? 0.18 0.54( O.05 0.69( 0.23 4.50 0.40 I t 0.19,1 0.30 1 0.04 1 3 0.16) 1/78 Discharge 1 0.07 0.11 0.49 0.05 0.56 0.16 4.03 0.40 5.40 2 0.11 0.65 0.76 3 Cont rol 1 0.07 0.14 0.41 0.01 0.48 0.14 3,40 0.05 2 0.12 0.10 0.78 0.07 0.91 0.17 6.45 0.55 3 0.11 0.20 0.08 0.08 0.19 0.28 0.70 0.65 " Not determined. 64
TABLE B-4. Percentage of organic carbon and calcium carbonate in bedload sediments collected rear the Diablo Canyon Nuclear Power Station. Date Site Organic carbon Inorganic carbon Total carbon Calcium carbonate Intact <150 pm Intact <150 pm Intact <150 pm Intact <150 pm 6/77 Discharge 1 0.81 5.11 4.53 1.73 5.34 6.84 37.76 14.2 8/77 Discharge 1 0.90 5.80 4.15 1.97 5.05 7.77 34.56 16.0 i i i 10/77 Discharge 1 1.07 3.91 4.98 33.0 38.1 lp I 2 0.75l 6.63 4.58[ 2.14 5.33 [ 8.77 17.8 3 1.20 4.59 5.78 38.2 l 65
TABLE B-5. Particle size of bedload sediment collected near the San Onofre Nuclear Power Station. f Intact bedload sediments Bedload Sediment s (<150pm) Date Site Size ($) Skewness Kurtosis Size ($) Skewness Kurtosis 4/4/77 Discharge 1 0.55 0.03 0.34 3.69 0.11 -0.79 Control 1 1.04 -0.57 6.23 3.72 -0.84 4.04 5/5/77 Discharge 1 2.93 0.08 -0.53 3.35 0.83 0.89 Control 1 1.57 -0.26 8.36 3.49 -0.84 1.58 7/21/77 Discharge 1 2.82 -0.69 -0.84 2 3.39 -0.66 3.67 3 1.51 -0.06 1.08 Control 1 0.96 0.25 1.43 2 2.50 0.49 -0.82 3 3.69 -1.28 3.28 10/18/77 Discharge 1 1.37 0.82 2.57, 2 0.98 0.22 0.69 3.65 2.20 15.60 l 3 3.53 3.91 33.37 Control 1 2.62 1.10 3.83, 2 1.20 1.78 9.34 3.95 3.51 22.82 l 3 3.90 2.38 18.26 / l 1/78 Discharge 1 0.76 0.46 7.67 3.38 0.68 19.61 l 2 1.62 0.96 7.23 3.81 2.47 15.13 l 3 I Control 1 2.03 0 1.14 l l 2 1.56 0.75 3.45 3.89 2.40 19.98 3 3.80 0 9.87 3.86 3.00 19.33 8 Not determined. 66
.WC Focu ZS RS. NUCLEAR RECULATOctY COMMISSION (7 77) NUREG/CR-1090 l BIBLIOGRAPHIC DATA SHEET UCRL-52555 4.T TLE AND SuaTITLE (Add VosmeIsa. itopprepnere1
- 2. (tene blaa4 Copper Distribution in Abiotic Compartments of Aquatic
- 3. RECIPsENT'S ACCESSION NO.
Ecosystems Adjacent to the Diablo Canyon and San Onofre Nuclear Power Stat innc:
- 7. AUTHORISI
- 5. DATE REPORT CGMPLE TEO MONTH l YEAR R. R. Emerson and F. L. Harrison September 1981
- 9. PERFORMING ORGANIZATION N AME AND MAILING ADORESS (factude Zip Code)
DATE REPORT ISSUED l YEAR MONTH Lawrence Livermore National Laboratory October 1981 P.O. Box 5507 6' ~' #" " Livermore, California 94550
- 8. (Leur b!nki
- 13. SPONSORING ORGANIZATION NAME AND MAILING ADDRESS (include Zip CodsJ
- 10. PROJE CT/ TASK / WOR.< UNIT NO.
Division of ilealth, Siting and Waste Management j Office of Nuclear Regulatory Research it. CONTR ACT NO. U.S. Nuclear Regulatory Commission Washington, DC 20555 FIN A0119
- 13. TYPE OF REPORT PE Rioo COVE RE o (inclusied derrs/
Technical l
- 15. SUPPLEMENTARY NOTES
- 14. (Leu, umk/
I
- 16. A95 TRACT (200 words or /sss) l Copper concentrations were measured in samples of seawater, suspended par'ticles, and bedload sediments collected in intake and discharge areas of the San Onofre and Diablo Canyon Nuclear Power Stations. At the San Onofre Power Station, whose cooling system has half copper-nickel and half titanium tubing, the copper in the water col,umn during normal i
operation ranted from 0.8 to 3.3 ug/L (micrograms per liter). At the Diablo Canyon Power Station, whose cooling system has only titanium tubing (except that in an auxiliary system) l copper concentrations ranged from 0.6 to 2.3 ug/L. The San Onofre Station has a long operational history, but the Diablo Canyon Station has never generated electricity. Copper concentrations in effluent waters at San Onofre were usually somewhat higher than those in control and intake areas. Five minutes after start-up of the main circulators at Diablo Canyon, the copper concentration in the effluent water was about 28 pg/L, but decreased rapidly and reached normal levels after about 3 h. Average copper concentrations in intact bedload sediments were 4.4 pg/g at San Onofre and l 10.4 p /g at Diablo Canyon. We noted considerable. spatial heterogeneity both at the control g i and discharge areas, and higher copper concentrations in the (150-um fraction than in intaci sediments.
- 17. MEY WORDS AND DOCUMENT ANALYSTS 17a. DESCRIPTOnS coppe r nuclear stations sediments marine waters 17b. IDENTIFIERSIOPEN ENDED TERMS l
- 18. AVAILABILITY STATEMENT
- 10. SECURITY CLASS (This reporTJ
- 21. NO. OF PAGES Unclassifled Unlimited
- 22. P RICE
- 20. St ggYgg(Th,s py) d NRCFoau 335 87.77)
I
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