ML19345D242
| ML19345D242 | |
| Person / Time | |
|---|---|
| Site: | San Onofre, Diablo Canyon  |
| Issue date: | 11/30/1980 |
| From: | Bishiop D, Bishop D, Emerson R, Harrison F LAWRENCE LIVERMORE NATIONAL LABORATORY |
| To: | |
| References | |
| CON-FIN-A-0119, CON-FIN-A-119 NUREG-CR-0750, NUREG-CR-750, UCRL-52706, NUDOCS 8012120308 | |
| Download: ML19345D242 (66) | |
Text
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NUREG/CR-0750 UCRL-52706 RE
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Concentration and Speciation of Copper in Waters Collected Near the San Onofre and Diablo Canyon Nuclear Power Stations Manuscript Completed: August 1980 Date Published: November 1960 Prepared by F. L. Harrison, d. J. Bishop, R. R. Emerson, and D. W. Rice, Jr.
Lawrence Linrmore National Laboratory 7000 East Avenue Livermore, CA 94550 Prepared for SAFER Division Office of Nuclear Regulatory Research U.S. Nuclear Regulatory Commission Washington, D.C. 20555
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NRC FIN No. A-0119 l
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ABSTRACT Concentrations and physicochemical forms of copper were determined in seawater collected in the intake and discharge areas of the San Onofre and Diablo Canyon Nuclear Power Stations. At the San Onofre Station, which has half copper-nickel and half titanium tubing in its cooling system, 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, which has only titanium tubing in its cooling system (except for 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, whereas the Diablo Canyon Station has never generated electricity.
Copper concentrations in effluent waters at San Onof e were usually higher than those in waters from control and intake areas, but differences were small. During start-up of water circulation through the condensers at Diablo Canyon after a previous shutdown, a copper pulse was detected. Five minutes after start-up of the main circulators, the copper concentration in the effluent water was about 28 pg/L, but decreased rapidly and reached normal levels after about 3 h.
Copper in the particulate fraction of the discharge waters ranged from less than 10 to 75% of the total. Copper in the so';51e fraction was primarily in bound forms. The apparent complexing capacity was approximately 1 pg Cu/L; soluble organics ranged from 1.2 to 2.5 mg C/L.
64'u indicated Ultrafiltration of discharge waters radiolabeled with C
that, in most samples, less than 20% of the copper was in chemical fo ms reported to be available to biota. Copper complexation appears to involve organic matter of >1000 and <100,000 molecular weight range.
To better document the effects of the use of copoer in cooling systems, we recomend that more information be obtained on the concentrations and the chemical. forms of copper in discharge waters during start-up, on the quantities of labile and bobnd copper in waters during chlorination, and on the identity of and seasonal changes in concentr'tions of soluble organic matter that complex copper.
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CONTENTS Abstract
. iii Foreword xi Executive Summary.
.xiii Techniques.
.xiii Findings.
.xiii Recommendations for Further Study
. xv1 Effects of Start-up.
. xv1 Effects of Chlorination
. xvi Seasonal Changes in Complexation to Organic Matter.
. xvii Introduction 1
Chemistry of Copper.
1 Physicochemical Forms of Copper in Seawater 2
Copper Toxicity 3
Literature Review 3
Research Objectives 4
Material and Methods 5
Site Characteristics 5
San Onofre Nuclear Power Station.
5 Diablo Canyon Nuclear Power Station.
7 Seawates Collections 7
San Onofre Nuclear Power Station.
7 Diablo Canyon Nuclear Power Station.
9 Reagents 10 Copper Analyses 10 Ion Exchange Analyses 10 Solvent Extraction of Copper Chelates 12 Differential Pulse Anodic Stripping Voltammetry (ASV).
13 Apparent Complexing Capacity.
14 Ultrafiltration 14 Organic Carbon Analyses 16' v
A
Results and Discussion 17 Total Copper Concentrations in the Water 17 Soluble and Particulate Copper Concentrations in the Water 20 Soluble Copper Species 22 4
Apparent Complexing Capacity 27 Ultrafiltration 31 Conclusions.
40 l
References 43 Glossary 51 Appendix A 53 Appendix B 55 vi m
_~ _
LIST OF ILLUSTRATIONS 1.
San Onofre Nuclear Power Station study area.
6 2.
O bblo Canyon Nuclear Power Station study area.
8 3.
Diagram of the Chelex-100 ton exchange separation process 11 4.
Ultrafiltration procedure flow diagram 15 5.
Voltamograms obtained with aliquots of sample water to which increasing amounts of copper were added 30 6.
Diagramatic representation of apparent complexing capacity.
30 Bl. Amicon ultrafiltration system 64 LIST OF TABLES 1.
Chemical species of copper xiv 2.
Copper concentrations (pg/ liter) in waters collected in the vicinity of the San Onofre Nuclear Power Station 18 3.
Copper concentrations (pg/ liter) in waters collected in the vicinity of the Diablo Canyon Nuclear Power Station 19 4.
Soluble and particulate copper concentrations (pg/ liter) in seawater collected frot:: waters adjacent to the United States 21 5.
Concentrations of soluble copper species (pg/ liter) in waters collected in the vicinity of the San Onofre Nuclear Power Station.
23 6.
Concentrationsofsolublecopperspecies(pg/ liter)inwaters collected in the vicinity of the Diablo Canyon Nuclear Power Station. 24 7.
Concentrations of labile and bound species of copper (pg/ liter) measured in seawater collected at different locations.
26 8.
Apparent complexing capacity of water collected in the vicinity of the San Onofre and Diablo Canyon Nuclear Power Stations.
29 vii e.
64 9.
Percentage of Cu in molecular weight fractions in ultrafiltered seawater 32 64
- 10. Percentage of Cu in molecular weight fractions in ultrafiltered seawater 33 64
- 11. Percentage of inorganic-and organic-bound Cu in the intermediate molecular weight fraction (>1,000 <100,000) of discharge water 35 64
- 12. Percentage of Cu recovered in the dissolved (filtrate plus solution remaining in the ultrafiltration cell) and sorbed (to the walls and membrane of the ultrafiltration system) fractions.
36 64 B-1. Percentage of Cu recovered in the different components of the system after ultrafiltration of seawater through 0.4-pm pre filters (SanOnofre, 10/18/77).
56 64 B-2. Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-pm filtered seawater (DiabloCanyon,6/7/77).
57 64 B-3. Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-um filtered seawater (SanOnofre,7/21/77) 58 64 B-4. Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-um filtered seawater (Diablo Canyon, 8/11/77) 59 64 B-5. Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-um filtered seawater (Diablo Canyon, 10/12/77).
60 64 B-6. Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-pm filtered seawater (SanOnofre,(intake) 10/18/77).
61 viii
i 64 8-7. Percentage of Cu recovered in the different components of the system after ultraffitration of 0.4-pm filtered seawater (SanOnofre,1/10/78) 62 64 B-8. Calculated concentrations of Cu (pC1/ml) in 0.4-um filtered seawater (San Onofre, 10/18/77).
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FOREWORD This study is part of a larger research project that has three purposes:
)
(1) to study the behavior of potentially toxic substances introduced into surface waters from nuclear power stations, (2) to determine the magnitude of the impact of these substances on representative economically important aquatic species, and (3) to develop models to predict the behavior and impact of these discharged substances. The initial thrust of the research has been directed toward investigating the impact of cooling systems' corrosion products, in particular those of copper. Copper is of special interest because of its documented toxicity to aquatic organisms.
This investigation was funded by the Office of Nuclear Regulatory Research, Division of Safeguards, Fuel Cycle and Environmental Research, under FY 1976 Nuclear Regulatory Research Order No. 60-76-144.
The authors thank Jack Dawson for his assistance in collecting and processing field samples and Dr. James Katekaru and P. Edward Pullen for their assistance in the polarographic analyses.
We are indebted also to Brown and Caldwell Consulting Engineers for allowing us to accompany their staff members on field trips at San Onofre and to use their boat and equipment, for the sample collected by their SCUBA divers, and for the field experiences shared by their research staff.
We wish also to thank the staff of the Pacific Gas and Electric Company and the Southern California Edison Company for their assistance in coordinating the collection of samples and for advice and background information. Their cooperation and support made this study possible.
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EXECUTIVE
SUMMARY
Field studies were performed at the Diablo Canyon and San Onofre Nuclear Pos.er Stations to determine the quantities and physicochemical forms cf copper released into the adjacent water from the copper-nickel tubing used in the cooling systems.
San Onofre has a long operational history, whereas Diablo Canyon has never generated electricity. Data on copper are critical for an assessment of its rate of dispersion in the ecosystem, rate of interaction with other pollutants, final distribution, and toxic effects on the biota.
TECHNIQUES Several analytical techniques were used to identify the forms and quantities of copper present in the seawater. We measured total copper by organic solvent extraction of copper chelates and by differential pulse anodic stripping voltametry (ASV). Total soluble and particulate copper was detennined after separating the fractions by filtering the water through membranes with 0.4-um pores. Labile copper in the soluble fraction was measured by ion exchange techniques and ASV. The apparent complexing capacity was determined by quantifying the ASV-labile copper after copper additions.
Ultrafiltration indicated the molecular weight distribution of the copper species and the effect of dissolved organic matter on distribution. Table 1 summarizes the kinds and weight ranges of copper species that may be present.
FINDINGS Total copper in the discharge water during normal power station operation at San Onofre was slightly higher or not significantly different from that in 4
the intake and control waters. Measured concentrations ranged from 0.8 to 3.3 pg Cu/L at San Onofre and from 0.6 to 2.3 at Diablo Canyon. These concen-trations were below those values reported to elicit a detectable response in most marine organisms. However, our studies and those of Warrick et al.
xiii A
TABLE 1.
Chemical species of copper.
Species:
Free'.
Inorganic ton Organic complexes, Metal species Metal species in Metal species Precipitates, metal
, pairs; inorganic chelates-bound to high
. the form of highly sorbed on organic particles, ions complexes' molecular wt dispersed colloids colloids remains of living 8
organic material organisms Examples:
Cu +,q,.Cu(OH)f*
2 b
Cu-SR Cu-lipids Cu(OH)n-Me(OH)n u(OH)n, Cuco,
3 2
Cu-00CR Cu-humic-acid CuS, etc. on D"
clays.
Cuc03
' Lakes" "Gelbstoffe" Cu-polysaccharides Filterable 1
7m :Aion:
Olametertige 12.5k 15E 52k Molet. alar weight <1000
>1,000 <10,000
>10,000 400,000
>100,000 a Modified from Stten and Brauner (1975).
b R = organic ligand.
g
(1975) show that copper concentrations measured after start-up of cooling water through nuclear power stations following a shutdown are at toxic levels for some organisms.
Copper measured in the particulate fraction of the water ranged from less than 10% to 75%. More data are needed from both San Onofre and Diablo Canyon to establish a pattern among sampling sites or among seasons.
In the soluble fraction of the discharge water, more than 60% of the copper was bound in almost all samples. Although the ASV and Chelex-100-labile upper values were not the same, both confirm that a large fraction of the copper is in bound forms. The exceptions were those samples collected from the discharge waters after start-up of the cooling system.
The apparent complexing capacity of discharge waters from both sites was low, approximately 1 pg Cu/L. This indicates that labile copper added to the discharge waters in excess of 1 pg/L remains labile and is toxic to the biota.
The concentrations of soluble organic carbon in the water ranged from 1.2 to 2.5 mg C/L and did not appear related to apparent complexing capacity.
It appears that a significant fraction of the soluble crganic matter is not involved in forming tightly bound copper complexes.
Ultrafiltration of San Onofre and Diablo Canyon discharge waters 64 radiolabeled with high-specific-activity Cu indicated that, in most 64 samples, less than 20% of the Cu is in the <1,000 molecular weight fraction--the weight fraction containing most copper species that are 64 l
considered toxic to the biota. The percentage of Cu in the various molecular weight fractions changed substantially with UV treatment of the
~.ater.
Important results of the UV treatment are as follows:
(1) the percentage in the small molecular weight fraction (<1,000) increased.
(2) the percentage in the high molecJar weight fraction (>100,000) increased in most tests.
(3) the percentage in intermediate fractivas (>1,000 but <100,000) decreased in rra-ly all tests.
(4) the percentage sorbed on the walls and membrane increased.
(5) a significant portion of the copper complexation appears to involve dissolved organics in the molecular weight range of >1,000 to <100,000.
xV n
To better document tha effects of using copper in cocling systems, we recomend that more information be obtained on the concentrations and chemical forms of copper in discharge waters during start-up, on the quantities of labile and bound copper in waters during chlorination, and on the identity of and seasonal changes in concentrations of soluble organic compounds that complex copper.
RECOMMENDATIONS FOR FURTHER STUDY EFFECTS OF START-UP The highest copper concentration in our field studies at Diablo Canyon and San Onofre Nuclear Power Stations was measured after water started circulating through the cooling system at Diablo Canyon. The 28 pg Cu/L measured after start-up was low compared to the 1800 and 7700 pg Cu/L reported earlier (Warrick et al.,1975) because the copper-nickel alloy in the main cooling systems was replaced by titanium; the only copper now present is in a small auxiliary system. Most of the copper in the water was labile, the chemical form highly toxic to biota.
It is not known whether the high concentrations observed after start-up at Diablo Canyon are unique to that power station or are a general phenomenon. Changes in the concentrations and chemical forms of copper l
discharged at other power stations must be documented to assess the impact of continued use of copper-nickel alloys in cooling systems and to determine the need for countermeasures.
EFFECTS OF CHLORINATION Water is comonly chlorinated to reduce fouling of the condenser tubing in the cooling systems. This practice may affect the biota directly (as free chlorine or its reaction products) or indirectly (by affecting the chemical form of potentially toxic metals in the discharged water). Because the chemical form of copper critically affects its toxicity to the biota and its partitioning among abiotic compartments, more information is needed on the quantities of labile and bound copper in the water during chlorination.
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SEASONAL CHANGES IN COMPLEXATION TO ORGANIC MATTER Our ultrafiltration results indicate that dissolved organic matter plays an important role in determining the chemical form of copper in water, but little information is available about the quantities of organic matter involved in copper binding and how these vary with season. This organic matter must be characte-ized more precisely so that the source can be identified and isolati Organic matter could be added to effluent waters during start-up to minimize the impact of releasing labile copper.
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_d.
INTRODUCTION The environmental impact of using surface waters to cool the condenser systems of nuclear power stations is related to the quantities and physico-chemical forms of the metal corrosion products discharged. Of special interest are the corrosion products of copper, because Cu-Ni alloys have been used extensively in the cooling systems of power stations and because aquatic organisms are reportedly sensitive to increased levels of labile species of copper released in the water.
CHEMISTRY OF COPPER Copper's behavior in aquatic ecosystems depends primarily on its chemical properties. Copper has a single electron in the 4-s shell, outside a completed 3-d shell. Because of its d electrons, it belongs to the main group of transition elements. An important characteristic of these elements is their ability to form complexes, or coord' nation compounds, with a number of neutral molecules, or ligands. The d orbith'; project well out to the periphery of the atoms and ions so that the electrons occupying them are strongly influenced by the surroundings of the ion and, in turn, are able to signifi-cantly influence the environment. Therefore, many properties of the ion are quite sensitive to the number and arrangement of d electrons present.
Copper has two main oxidation states:
+1 and +2.
The +3 oxidation state is known in solids such as Cu 0, but such compounds.are powerful oxidizing 23 agents in water and are not stable. Only the +2 state will be considered here, because in aquatic systems most cuprous compounds are oxidized readily to Cu(II), but further oxication to Cu (III) is difficult.
In binding, the cupric ion has coordination numbers of 4 and 6 (a coordi-nation number is the total number of anions or molecules directly associated withthecation). The shape, or symmetry, of its coordination sphere is square planar for coordination number 4, and distorted octahedral for coordi-nation number 6.
Copper binds strongly tc the -NH2 and -SH groups of organic ligands and, to a lesser degree, to -OH groups.
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i PHYSIC 0CHEMECAL FORMS OF COPPER IN SEAWATER The physicochemical forms of copper present in seawater may be numerous.
Copper released into the water column is partitioned between the soluble and particulate fractions. The form in the soluble fraction is related to the inorganic and organic constituents in the water; the form in the particulate fraction is related to the kinds of sinks present on the particles.
The physicochemical form of copper is of major importance in determining its role in the sedimentary cycle and in pollutant interaction and its availability and toxicity to the biota (Stunun and Brauner,1975; Jenne and Luoma,1978). F crence and Batley (1976) have disputed the common practice of relating toxicity to the total concentration of a particular metal in water rather than to the toxic species.
(The term " species" refers to the actual form in which a molecule or ion is present in solution.)
The species of copper in the soluble fraction have been classified as labile or bound (Batley and Florence,1976) and as very labile, moderately labile, slowly labile, and nonlabile (Figura and McDuffie,'1979). The groups are defined by the experimental conditions under which the measurement is made. Techniques used to differentiate between copper species include solvent extraction (Brooks et al.,1967; Kinrade and Van Loon,1974; Kremling and Petersen, 1974; Flett, 1977), ion exchange (Riley and Taylor, 1968; Florence and Batley, 1977), electrochemistry (Florence, 1970; Chau and Lum-Shue-Chan, 1974; Gardiner and Stiff, 1975; Florence and Batley, 1977; Lund and Onshus, 1976; Nurnberg et al., 1976; Sugai and Healy, 1978), ultrafiltration (Rashid, 1971; Smith, 1976), gel filtration chromatography (Sugai and Healy, 1978), and ion specific electrodes (Williams and Baldwin, 1976; Sunda and Guillard, 1976; Sunda and Lewis, 1978).
In this report, for convenience, we will continue to use the term: labile and bound as proposed by Florence and Batley (1976) even though they are imprecise. We shall refer to the following as labile l
species:
ions, ion pairs, readily dissociable (labile) inorganic and organic complexes, and easily exchangeable copper adsorbed on either colloidal l
inorganic or organic matter.
Inorganic anions to which the copper may be complexed are hydroxides, carbonates, chlorides, sulfates, phosphates, and nitrates: organic anions are amino acids, amino sugars, alcohol, urea, etc.
We shall refer to those forms that are slowly reversible or irreversible as i
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a
bound species: stable metal-organic complexes, metals bound to high 11ecular-weight organic material, some inorganic complexes, and metal occN' or sorbed tightly on, highly dispersed colloids.
Included in this group of bound species is a large fraction of copper complexed to humic substances (refractory organic material that comprises approximately 90% of erganic material in water).
COPPER T0XICITY Metal chelation has been shown to be an important control mechanism for toxicity to aquatic organisms (Steeman Nielsen and Wium-Anderson,1970; Lewis e_t_ al., 1971, 1973; Davey e_t_ al.,1973; Morris and Russel,1973; Black,1974; t
Pagenhopf et al.,1974; Jackson and Morgan,1978; Sunda and Guillard,1976; Sunda and Lewis, 1978; Sunda and Gillespie, 1979). For copper,.the detoxification in seawater appears to be related to the stability constant of the copper chelate (Harrison et al., 1980a). Because the chemical form affects the availability of copper to biota, identification of the chemical species is critical for evaluation of the toxic response.
LITERATURE REVIEW Information on the concentrations and physicochemical forms of copper in seawater before and after passage through copper-nickel cooling systems is limited. Alexander (1973) obtained data on what he referred to as reactive, total soluble, and total particulate copper concentrations in water discharged from the Northport Power Station of the Long Island Lighting Company. His data show that-only a fraction of the released copper was in the reactive form.
Copper concentrations in effluent waters of the Diablo Canyon Nuclear Power Station of the Pacific Gas and Electric Company were measured during a series of start-ups from June-28 to October 24,1974 (Warrick et al.,1975).
These data were obtained before the copper-nickel tubing in the cooling system was replaced with titaniua. Only total copper was measured. These measurements ranged from 1 to 7,700 pg Cu/L and depended on the amount of time that had lapsed since start-up.
3
(
Dorband et al. (1976) measured the concentrations of soluble (<0.45 pn) and particulate (>0.45 un) copper in the influent and effluent waters of the Southern California Edison Company's Encino Power Station at Carlsbad, California. In most sampling periods, the copper concentrations in both the soluble and particulate fractions were higher in the effluent than influent l
waters.
Young et al. (1977) investigated the levels of trace metals in cooling waters from eight coastal power stations discharging into the Southara California Bight. The mean copper concentration in effluent waters from the eight power stations was higher than the mean concentration of the influent.
RESEARCH OBJECTIVES This investigation was initiated to obtain more information about the quanti-l ties and physicochemical forms of copper released into seawater from nuclear power station operations. Sampling programs were conducted at the nuclear power stations at San Onofre and Diablo Canyon in California. Water samples collected during different seasons of the year were analyzed for copper by state-of-the-art methods. Analyses were performed to determine the total amount of copper present and the quantities in the soluble (<0.4 un) and particulate (>0.4 un) fractions.
In the soluble fraction of the water, the amount of copper in the labile and bound forms and the apparent complexing capacity were determined. In addition, the filtered water was ultrafiltered to obtain an indication of the molecular weight distribution of the copper species and of the effect of dissolved organic matter on their distribution.
Regits from this investigation will provide information on speciation that_is l
needed to understand the behavior of the copper released. Thus, its temporal and spatial distribution can be determined and its potential effects on biota evaluated. These data are needed to assess the environmental impact of corrosion p"aducts from power station cooling systems.
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MATERIAL AND METHODS SITE CHARACTERISTICS San Onofre Nuclear Power Station The San Onofre Power. Station is located between San Clemente and Oceanside in Southern California. Unit 1 uses a pressurized water nuclear reactor and has a gross electrical output of 456 MW. Field samples were collected primarily in the immediate vicinity of Unit 1.
Currently in Unit 1, half of the tubing is of copper and nickel (90:10) and half is titanium. The seawater intake is located approximately 980 m offshore and at a depth of 8 m (Fig. 1).
The intake conduit is 3.7 m in diameter and is fitted with a velocity cap to reduce the entrapment of marine organisms. Effluent is discharged through a single vertical structure approximately 792 m offshore and at a depth of 7.3 m.
The discharge of the surface-oriented thermal plume results in a bubble formed in the vicinity of the offshore discharge (outfall). The mean daily pump flow 1s about 480 MGD.
Field samples were always collected from the outfall region.
In July, October, and January, samples were collected also from a control site 6.7 km south of the outfall and from either the plant intake or offshore intake. The number and approximate size of the samples collected differed with the field survey (Table 1). The station was in normal operation during the collection periods (J. Stock, private communication, 1978).
Dredging for the conduit lines of the new units (2 and 3) was in progress throughout the year near the discharge site. January-sampling was conducted during an intense storm along the Southern California coast.
At a given collection time, the temperature of the water at the outf all varied with depth; the surface water was about 2 to 3 C warmer than the 0
bottom water. Temperature at the surface ranged from 14 to 22 C depending on the season. The salinity of the water collected during 1977 averaged 33.5
+ 0.5 /oo. The pH ranged from 7.7 to 8.1.
5
an Onofre Creek San Mateo Creek Las Flores Creek San Onofre State Beach San Onofre Nuclear Power Station
,r - - - ---------- - - - - -- - -,g San Ono f-e S ta te Beach
.T N
g 1 ~
g'eq 4
Outfall
\\_
N 7
G
\\-
9rn
/
--San Onofre kelp Barn kelp )' C2r San Mateo kelp
---~~'%
D Control 18 m cn
~~
7 (22 south) 5 -
x n
O.5 b O5 mi w
0.50 1 km FIG. 1.
San Onofre Nuclear Power Station study area.
Diablo Canyon Nuclear Pow:r Station The Diablo Canyon facility is located about 11 km north of Avila, California, and about 18 km south of Morro Bay, California.
Intake waters were collected from the cove behind the breakwater (Fig. 2). Effluent from the cooling system cascades 20 m down a three-step weir into Diablo Cove. The cooling water system for Unit I requires two cooling water pumps that together 3
circulate 3280 m of seawater per minute through the condenser tubes. The 90:10 copper-nickel condenser tubing originally installed in the system was replaced in 1975 with titanium tubing. However, some 90:10 copper alloy is still present in an auxiliary cooling system.
Three field samplings were made at the facility (Table 1). Samples were not collected under normal operating conditions because power production had not been initiated. However, water was circulated through the condenser system for test periods of different durations before and af ter the change in 1975 from copper-nickel to titanium cooling tubes.
In October 1977, after a 4.5-mo shutdown, we collected effluent at various times following start-up of the Unit 1 cooling wMer sy!. tem. The samples were collected from the effluent stream just before its discharge into Diablo Cove.
The temperature of the water at the time of collection ranged from 11.9 to 13.7 C.
Lower temperatures at Diablo Canyon than at San Onofre were expected because the reactor was not operating and temperatures are icwer north of Point Conception than in the Southern California Bight. The salinity 0
averaged 32.9 1 0.1 /oo and the pH 7.8 1 0.1.
SEAWATER COLLECTIONS San Onofre Nuclear Power Station Seawater from the offshore intake, discharge, and control sites was sampled from a boat. We anchored over the area of interest and used a peristaltic pump to obtain seawater from approximately 2 m below the surface; at the discharge site, the water was' taken from the bubble. The water was filtered M situ through 0.4-um (pore size) Nuclepore 190-mm (diameter) membrane filters. Before use, the plastic tubing and filter holder were acid-7 l
Power station g,,q
)
,1ge;$%,
ll O 'D Meteorological tower
~
o Cooling water discharge
\\s g D, s'
'e, s'4 s\\ h
}
,s* e ss s
's's'Oq co
\\N h 1
4 s.
~
Diablo Cove C Cooling water 1
intake East breakwater
'l.
Diablo Rock We<'. breakwater
)
~
^
Pacific Ocean d
250 50 1000 ft l H 0
50 100 150 200 250 m 1
FIG. 2.
Diablo Canyon Nuclear Power Station study area.
wash::d and rinsed with doubly (glass) distilled water (DDW). Because of the difficulty of establishing differences among stations when the copper concen-trations are only a few parts per billion, extreme care was taken to keep the equipment and sample free from contamination. The containers used to transport samples were carefully cleaned (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 caps clean and to prevent extraneous material from entering the sampling containers. The bottles were sealed in the field innediately after the sampling was completed, enclosed in plastic bags, and shipped in crushed ~;e to Lawrence Livermore National Laboratory (LLNL). Samples were received at LLNL between 4 to 10 h after they were collected.
At each sampling station, one sample of filtered water was acidified to pH 1 with hcl; acidification reduces sorption to walls. These samples were used to determine total soluble copper.
Filter holders were purged of water before the filters were removed.
Filters were placed in plastic bags for shipment to LLNL. The volume of water that passed through each filter was recorded.
For analysis of organic carbon, unfiltered seawater samples were collected 0
in precombusted, 450 C, glass bottles by a SCUBA diver at a depth of about 2 m.
These samples were stored in ice chests and returned to LLNL.
Immediately after arrival they were filtered through precombusted glass fiber filters.
Diablo Canyon Nuclear Power Station Water from the intake cove at Diablo Canyon was collected from a boat by the same method as described for the sampling at the San Onofre Power Station.
During one sampling period, water was collected off the end of the dock, which extends into the intake cove.
Samples of effluent were collected directly from the sump pump at the base of the discharge tunnel; no boat was required.
9 i
REAGENTS J. T. Baker Ultrex-grade nitric, perchloric, and hydrochloric acids were used throughout. Doubly (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. Polypro-pylene and Teflon labware were, qed. 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 solution of amonium pyrrolidindithiocarbamate (APDC) and diethylamonium diethyldi-thiocarbamate (DDDC) ano the citrate buffar were extracted with MIBK. To remove copper from the 1% solution of APDC-DuDC, 10 ml MIBK was added to 100 ml solution, the mixture shaken for 10 min, and the organic phase discarded.
The citrate buffer 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.
CCPPER ANALYSES P
Ion ?xchange Analyses The Riley and Taylor (1968) method was used to determine copper bound to the Chelex-100 resin. The filtered water samples were processed imediately after arrival at LLNL. The pH of the water was not altered. Each 8-L carboy was fitted with tubing to permit the water to be gravity-fed into a 15-m-diameter column and packed to a height of 25 m witF. Chelex-100 resin (Fig. 3). The rate of flow of water through the column did not exceed 5 ml/ min; flow rate was adjusted by altering the height of the carboy. After the water sample had passed through the column, the column was eluted with two l
10-ml aliquots of 2 N HNO to collect the species of the copper bound to the 3
j resin and the eluant diluted up to volume in a 25-ml volumetric flask.
10
F atersample W
( w Column effluent Cheiex-100 ti O
T
/-
A
\\
io oi l
//
4
+
C s
io o i j
FIG. 3.
Diagram of the Chelex-100 ion exchange separation process.
Procedural blanks were run with each set of samples from a power si.ation.
Columns were eluted with acid and the eluant diluted to volume as described above. Average copper values of the blanks were subtracted from those of the samples. Total copper in the column blanks was low; the eluant contained 1.98 x 10-3 + 0.5 / 10-3 pg Cu/ml. This was usually <2% of the total copper in the sample eluant.
Each empty carboy was rinsed thoroughly with.25 ml of 2 N HNO. This 3
treatment removed copper adsorbed on the walls. Eluants from the columns and the acid rinses of the carboys were analyzed by direct aspiration into the flame of a Model 303 Perkin-Elmer Atomic Absorption Spectrometer (AAS) or by direct injection into a HGA 2100 model graphite furnace attachment to the AAS.
All standards were prepared in 2 N HNO
- 3 Because of the low levels of copper in the water, special care was taken in preparing the resin and the columns. The Chelex-100 resin was rinsed i
l 11 L
a
several times in DDW and the supernatant decanted, we thus discarded smaller resin beads. The impure sodium resin was cleaned and converted to the ammonium form before it was packed in a column. First, it was mixed with twice its volume of 2 N HNO3 and allowed to settle, and then the supernatant was discarded.
This acid treatment was repeated twice and followed by three rinses with DDW.
Next, the resin was mixed with twice its volume of 1 N NH 0H and allowed to 4
settle, and the supernatant discarded, Finally, the resin was rinsed three times with DDW.
Plastic columrs used in the determinations were cleaned by soaking in 2 N HNO for 24 h an rinsing with DDW. Clean resin in the ammonium form was 3
pipetted into washed columns to a height of about 2.5 cm with a clean plastic pipette. Talc-free gloves were used during cleaning and filling.
Solvent Extraction of Copper Chelates Total soluble copper was analyzed by methyl isobutyl ketone (MIBK) extraction of copper chelated by aninonium pyrrolidindithiocarbamate (APDC) and diethylamonium diethyldithiocarbamate (DDDC) (Kinrade and Van Loon,1974).
All samples were treated to reduce dissolved organic matter. They were acidified to pH 1 by the addition of concentrated hcl and 0.05 ml of 35%
H0 was added; samples were then boiled in a Teflon container for at 22 least 1 h.
A 200-ml aliquot of filtered seawater in a Teflon container was buffered with a citrate buffer, the pH adjusted to 4.8 - 5.0 with NH 0H, 4
5 ml of 1% APDC-DDDC solution and 40-ml MIBK added, and then the mixture was shaken for 1 min. Aliquots of the MIBK phase were removed directly from the MIBK layer and injected into the graphite-furnace attachment of the AAS for analysis. Standards were made daily in MIBK; 0.01 ml of an appropriate copper standard in 2 N HNO3 was added to 10-m1 MIFK.
For the blank samples, pure water was treated similarly to the seawater samples.
E ink samples contained 0.032 1 0.015 pg Cu; this was subtracted from the ar ant determined in each sample.
Copper recoveries were determined using known additions of CuCl 2 and 64Cu. The fraction of Cu recovered was 0.98 1 0.08, and the fraction for 64Cu was 0.95 1 0.03.
12 i
n
Differential Pulse Anodic Stripping Voltametry (ASV)
Another method used to determine copper was ASV (Florence and Batley, 1977). With this technique, copper is reduced at a potential more positive
- than the reduction potential (vs Ag/AgCl) and concentr3ted onto a mercury i
electrode. The amalgamated copper is measured by anodically stripping the copper from the mercury electrode by applying a potential ramp and measuring the current produced as the system reaches the oxidation potential of the copper. The anodic stripping current, i, is proportional to the equilibriu :
M concentration of the kinetically labile metal, i = kc (g +), where k is c
an empirical constant whose value depends on the electrode geometry and surface area, cell geometry, stirring efficiency, length of pre-electrolysis, scan rate of the linear stripping potential, and the diffusion coefficient of the copper, both in solution and in mercury (Sugai and Healy,1978).
Both labile and total copper in seawater were determined using a Princeton Applied Research 374 polarographic analyzer with a Hewlett-Packard microprocessor and X-Y recorder. The electrode system consisted of an Ag/AgCl reference electrode, a Pt counter electrode, and a hanging-mercury-drop working electrode. Prepurified N2 was used to purge samples of dissolved oxygen.
All measurements were made at room temperature (20 + 2 C)-
Analyses were performed in Polyethylene cups that had t,aen washed with nitric acid and rinsed with purified water. To determine labile copper concentrations, either 5 or 10 ml of seawater was added to the cup, the sample purged with N for 10 min, deposited for 6 min at -0.600 V, and then scanned 2
from -0.600 to 0.000 V or 0.100 V at a scan rate of 10 mV/s. A medium mercury drop size was used and the sensitivity was 1 A full scale. The naturally occurring chloride ions in seawater provided the supporting electrolyte.
Subsequent to the analysis for labile copper, each sample was acidified with 50 to 150 pl of perchloric acid to dissociate the copper ligands, digested for up to 2 h, and then analyzed for copper. Total copper concentration was determined by the standard additions method.
4 13
APPARENT COMPLEXING CAPACITY The complexing capacity was determined using the method of Chau et al.
(1974). Either 5-or 10-m1 samples of filtered seawater were placed into cups and then spiked with quantities of copper that would result in concentra-tions of added copper ranging from 0.25 to 8.0 pg/L. The spiked samples were equilibrated 15 to 18 h at 10 C, then a labile copper analysis was performed on each sample. The area of the copoer peak on each voltamogram was determined and plotted on the Y-axis,ersus concentration 2
of added Cu +. The complexing capacity of the sample corresponds to the copper concentration intercepted on the abscissa.
ULTRAFILTRATION 0
Two 2-L aliquots of filtered seawater that had been stored at 4 C since 64 collection (4 to 8 h) were spikeo with high specific activity Cu (20 pCi/g Cu), allowed to equilibrate a minimum of 12 h, and then subjected to 64 ultrafiltration (Fig. 4). The stable copper in the Cu spike cor tributed approximately 0.05 pg Cu/L to the seawater. This was generally less than 10%
of the total copper in the filtered water. After the 12-h equilibrium period, 64 the Cu serves as an effective tracer for the different species of stable copper present in the water at the time of collection.
One of the 2-L aliquots was photo-oxidized with UV light to reduce the concentration of dissolved organic matter. UV treatment destroys most effectively those molecules that strongly absorb UV irradiation. Two drops of 35% H 02 2 were added to each 100 ml of seawater to accelerate the oxidation.
The reaction rate was increased also by the increase in temperature that occurs during irradiation (60 C). Care was taken in the UV-irradiation step to I
avoid contaminating the samples. The quartz irradiation tubes were rinsed with 0.1 N hcl and then with DDW before use. To determine the loss of copper to l
the walls, aliquots taken before and after irradiation were counted for 64 64 Cu; in all samples, the Cu concentrations were lower after irradiation.
Ultrafiltration was performed with standard Model 402 cells, which
(
contained magnetic stirrers (Amicon Corporation, Lexington, Massachusett:,).
l Membranes used for the experiment were the XM-100A, UM-10, and UM-2 '.ypes i
14
J Ultrafiltration method Se.aater (pH 7.8) 1 Water + radionuclide (12 to 18 h)
Separation (Amicon membranes)
Radionuclide analysis Radionuclide analysis of filtrate of retained solution FIG. 4.
Ultrafiltration-procedure flow diagram.
1 l
15
(Amicon Corporation Diaflo). These membranes are made of complex, noncellulosic hydrous gels of inert polymers, which allow for retention of molecules above a specified molecular weight. The nominal molecular weight retentions of the membranes used in this test are as follows: XM-100A, 100,000; UM-10, 10,000; and UM-2, 1,000. The retention is related to the shape, as well as the size, of the molecules. For elongated molecules, the molecular weight cut-off is larger than the nominal one.
Some leaching of organic matter, due mostly to the glycerin protective coating applied by the manufacturer, occurs as these membranes are first used.
All membranes were pretreated to reduce organic material and metal contamina-tion. Under postive N2 pressure, 50 ml of 0.1 N hcl and 2 L of DDW were passed through the membranes sequentially. This procedure was adopted after monitoring the filtrates on a spectrophotometer at 200 pm and analyzig the filtrate for soluble organic carbon; the treatment resulted in adequate reduction in potentially interfering substances.
Each ultrafiltration experiment was initiated by transferring 270 ml of 64 the Cu-spiked seawater to an ultrafiltration cell. The seawater was stirred for 3 min, three 10-m1 aliquots were removed for counting, the remaining 240 ml was subjected to positive N2 pressure and constant stirring until 120 ml of filtrate was collected, and then the cell was vented. The 64 filtrate was sampled serially to monitor the changes in Cu concentration; a 10-ml sample was taken from each of the first, second, and third 40-ml aliquots of the filtrate. The solution remaining in the cell (retentate) was sampled only after venting. The cell assembly was rinsed well with 50 ml of 0.1 N hcl and a 10-ml aliquot of this acid wash was counted. Recovery of the 64Cu present in the initial test solution was calculated from the 64Cu concentrations in the different fractions.
ORGANIC CARBON ANALYSES Analyses for organic carbon were performed on the soluble and particulate fractions of seawater that had been filtered through precombusted glass equip-ment. The filter and filtrate were analyzed for particulate organic carbon and dissolved organic carbon, respectively, with an Oceanography International Carbon Analyzer by the standard persulfate oxidation method (Strickland and Parsons,1962).
16 n
RESULTS AND DISCUSSION TOTAL COPPER CONCENTRATIONS IN THE WATER The concentration of total copper in seawater in the vicinity of the San Onofre Nuclear Power Station was relatively low; the values ranged from 0.8 to 3.3 pg Cu/L (Table 2). Water discharged at the outfall was not significantly different or was slightly higher than that from the cont ol and intake areas.
The highest concentration, 3.3 pg Cu/L, was observed during January.
At Diablo Canyon, the concentration of total copper in seawater that had not circulated through the cooling system was low also; the values ranged from 0.6 to 2.3 pg Cu/L (Table 3).
Increased ccncentrattens in the discharge waters were seen imediately after water began to circulate on October 11, 1977.
Although titanium replaced the copper-nickel tubing in the main system at Diablo Canyon, part of the auxiliary pumping system still contains copper.
Our first sampla, taken about 5 min after the water began to flow, contained about 28 pg Cu/L. Copper levels dropped rapidly, and after 3.5 h little difference could be seen between the intake and discharge waters.
Literature values of copper concentrations in seawater differ with the site and time of collection. Schmidt (1978) in a review of copper concentra-tion in the marine environment gives a range of 0.06 to 6.7 ug Cu/L for open ocean areas; he states that copper concentration in water collected near shore are generally higher. Higher concentrations are generally found in areas receiving runoff from land or areas affected by man.
Some data on copper concentrations are suspect. Measurements may be too high because of impurities in added reagents; measurements may be too low because the analytical method used was selective for only some species of copper and inadequate care was taken to convert the copper in the sample to the species being measured.
Part of the scatter in data on copper is due to differences in source of the water mass. The distribution of copper in marine waters has been shown to correlate with the distribution of nitrate, a tracer of upwelling (Boyle and 17 p
TABLE 2.
Copper concentrations (ug/ liter) in t:aters collected in the vicinity of the San Onofre Nuclear Power Station.a Collection date Collection site Fraction Soluble Particulata Total April 4, 1977 Offshore discharge 1.5 May 5, 1977 Offshore discharge 0.2b 0.6 0.8 July 21, 1977 Control 0.6 Station intake 1.2
<0.1 1.2 Stati.on discharge 1.3
<0.1 1.3 Offshore discharge 0.8
<0.5 1.3 October 18, 1977 Control 1.0
<0.1 1.0 Offshore intake 1.0
<0.1 1.0 Offshore discharge 1.0
<0.1 1.0 January 9, 1978 Control 1.0 0.6 1.6 Offshore intake 1.6 Offshore discharge 1.8 1.5 3.3 aValues + 0.3 pg Cu/L.
64 bBased on the amount of a Cu spike that was recovered.
Edmond,1975). Copper is typical of dissolved species that are depleted in surface waters and enriched in deep waters. These investigators report about a factor-of-three difference in copper concentration with depth (0.06 to 0.21 ug Cu/L).
Increases in copper concentration in discharge waters after start-up have been reported previously at Diablo Canyon (Warrick et al., 1975). The highest concentrations reported was 7,700 pg Cu/L immediately after the main circula-tors started; concentrations after 10 min and 25 h of removed continuous operation were 900 and 67 pg /Cu/L, respectively. These investigators reported also that, in general, the longer the period between start-ups, the greater the amount of corrosion products that were fortned on the copper-nickel alloy surfaces.
The total copper contributed from power station cooling systems into the -
Southern California Bight is reported to be 2.1 metric tons per year (Young et 18 h
TABLE 3.
Ccpp;r cone:ntrations (pg/ liter) in waters collected in the vicinity of the Diablo Canyon Nuclear Power Station.
Collection Pumps Collection Fraction Total a
date site Soluble Particulate June 7, 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 Td
+
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 collected from intake cove.
cSample collected from effluent stream.
dTime zero, the time of initiation of water flow through the condenser, aj,.,1977). Although this is a considerable amount, it is smaller than Young etia],.(1977)reportedfromothersources. They estimated the input of copper in metric tons per year into the Southern California Bight from known sources to be the following: municipal waste, 507; antifouling paints,180; storm runoff, 42; dry fallout, 31. Although, in the total area of the Bight, the contribution from power station cooling systems is smaller than the others, this situation does not necessarily exist at power stations removed from man's influence and from rivers. Because of its isolated location on the coast, the input of copper to the Diablo Canyon ecosystem would be expected to be considerably larger from a copper-nickel cooling system than from other
- sources, i
l 19 l
i I
I
SOLUBLE AND PARTICULATE COPPER CONCENTRATIONS IN THE WATER The amounts of copper detected ;-; the soluble and particulate fractions of the seawater collected at both San Onofre and Diablo Canyon Power Stations differed greatly (Tables 2 and 3); the percentage in the particulate phase ranged from s10 to 75.
In June and August at Diablo Canyon, the copper was about equally distributed between the soluble and particulate phases, whereas ir October it was more than 90% in the soluble phase.
Insufficient data are available to establish a pattern among stations or among seasons at either site.
l Copper partitioning between soluble and particulate fractions has been l
measured in waters collected by other investigators at other locations (Table 4). The large differences in percentages in the particulate fraction from l
sample to sample observed at San Onofre and Diablo Canyon have been reported by others at other sites also. Young et al. (1977) measured the concentra-tions of soluble and particulate copper in influent and-effluent from eight power stations in the Southern California Bight that have copper-nickel cooling systems. They report a mean value for total copper of 1.12 ug/L for the influent waters and an increment of 0.31 pg/L for the effluent over the i
influent. These mean values were derived frem all the observations on all eight stations.
The particulate copper species were approximately 29% of the total copper in both the influent and effluent waters. The concentrations i
they reported for the particulate fraction may be lower than those reported by others; they leached the particles collected on the filters with acid rather I
than putting them totally into solution.
l Particulate material in the discharge waters may have be'en present originally in the intake waters, or may have been formed in the cooling system and added to the waste waters. Analyses were performed on the corrosion products cleaned out of the condenser tubes at Diablo Canyon (Warrick et al.,
1975). X-ray diffraction analysis indicated that the principal compound present in the corrosion product was a mixed copper salt, copper (II) trihydroxychloride [CuC1 2
- 3 Cu(0H)2
- 3 Soluble copper added to the circulating seawater from the c9oling system may not remain in solution but be sorbed onto particles. Our experiments in 64 the laboratory have shown that Cu distribution coefficients for illite are 20
TABLE 4.
Soluble and particulate copper concentrations (vg/ liter) in seawater collected from waters adjacent to the United States.
Soluble Particulate Location Reference fraction fraction 0.80 0.32 Power station intake Young et al. (1977) 1.01 0.42 Power station effluent, Southern California Bight 0.15-5.85 0.33-2.00 Power station intake Dorband g al. (1976) 0.15-4.60 0.33-3.24 Power station effluent, Southern California Bight 10 0.2 Florida Straits Alexander and Corcoran (1963) 20 0.2 Nearshore, Florida Alexander and Corcoran (1963)
Sargasso Sea Brewer and Spencer (1972) 1.39 0.40 to 7.90a Depth: 1 - 5069 m Florida Everglades Horvath et_ al. (1972) 2.6-6.7 0.5-4.1 Northeast Pacific Spencer et al. (1970)
Ocean Newport vessel repair hung et al. (1977) 8.6 harbor, California 0.57 Gulf of Mexico Slowey and Hood (1971) 0.17-1.1 (coastal) 0.25 Gulf of Mexico (open)
Slowey and Hood (1971)
(0-0.58) aConcentration at 3,232 m.
21
[
indeptnd:nt of stable ccpper concentraticns over thm ranga of concentrations 3
that have been reported in power station effluents (Emerson and Harrison, 1980). consequently, an increase in copper in the particulate fraction may not indicate a release of particulate copper, but only an increase in the amount of soluble copper sorbed to the particles already present in the water.
SOLUBLE COPPER SPECIES j
In the soluble phase, the distribution of copper between the labile and j
bound foms differed widely with sempling period at San Onofre (Table 5). The Chelex-labile copper is that fra: tion that binds to Chelex-100 ton exchange resin at pH 7.8.
The ASV-labile (differential pulse anodic stripping f
voltammetry-labile) copper is that fraction that is available for depctn into, and stripping'from, a hanging mercury-drop electrode at pH 7.8.
The concentrations of Chelex-and ASV-labile copper were not the same, as was expected, but both indicate that a large fraction of the copper was in bound foms in most water samples at the time of their collection.
4 At Diablo Canyon, most of the copper in the water samples was also in bound foms (Table 6). The exceptions were those samples collected from the-i discharge waters af ter water started circulating through the ' cooling system following the 4.5-mo shutdown.
In water samples, either an excess of copper (Cu) or of ligand (L) may be present; the forme.2ndition can he represented as (Cu + Cul) and the latter as (Cut + L). The samples collected at San Onofre and Diablo Canyon belong to the former category, whereas some of those at Saanich Inlet belong to the
}
latter (Sugai and Healy, 1978).
Under conditions comonly used in ASV, some chelated metals such as t
i Cu-EDTA are not reduced at the mercury electrode and, hence, are not measured, while others, like copper glycinate and copper-nitrilotriacetate acid-(NTA)..
are at least partially reduced (Brezonik et d., 1976). Chau et al. (1974)
{
measured the copper-binding capacity of several known complexing agents'such
}
as tartrate (log of the stability constant (log K's 5)), citrate (log K s 6),
. glycine (log K s 8), NTA (log K s 13), and EDTA (log K:S19)..They found that the technique measured only those copper-coniplexing agents with a log stchility
{
constant of >13.
Chelex-100, on the other hand, will remove quantitatively 4
-22 w
s-rw n,
ec.
-n
--a-
__-m_- -. _ _, -. - - - _ _.- -. _ _ _ _. _ _ _ _ _ -
TABLE 5.
Conctntraticns of solubic copp;r spicies (ug/ liter) in waters collected in the vicinity of the San Onofre Nuclear Power Station.
Collectiar.
Collection Total Chelex-100 ASV a
date site soluble Labile Bound Labile Bound April 4, 1977 Outfall 1.5 0.4 1.1 b
May 5, 1977 Outf all 0.2 0.2 July 21, 1977 Control 0.6 0.2 0.4 Plant intake 1.2 0.2 1.0 Plant discharge 1.3 0.4 0.9 Outf all 0.8 0.7 0.1 October 18, 1977 Control 1.0 0.2 0.8 0.0 1.0 Intake 1.7 0.2 1.5 0.2 1.5 Outfall 0.9 0.2 0.7 0.0 0.9 January 9, 1978 Intake 1.6 0.2c 1.4 0.7 0.9 d
Outfall 1.8 0.2 1.6 0.8 1.0 aASV analysis for total; values 10.3 ug Cu/L.
b ased on 64Cu recovery.
B cAnalysis of triplicate samples was 0.17 1 0.04.
dAnalysis of triplicate samples was 0.23 1 0.02.
only the copper complexes that have a lower affinity for copper than the resin (log K s 18). Kinetic considerations are importan't also. Retention on the resin depends on flow rate (Figura and McDuffie, 1979). Figura and McDuffie report that, under conditions where the flow rate through the column is > 0.3 m1' min, slow dissociation of the copper complexes results in low column retention values.
23 m
i
-TABLE 6. Concentrations of soluble copper spacies (pg/ liter) in waters collected in the vicinity of the Diablo Canyon Nuclear Power Station.
i Collection Collection Total Chelex-100 ASV date site solublea Labile Bound Labile Bound
[
June 7, 1977 Intake 1.9 0.1
-1.8 j
(Pumpsoff)
August 11, 1977 Discharge 0.5 0.1
'0.4 (Pumpsoff) t October 11, 1977 Intake Tb + 120 min 1.2 0.4-0.8 Discharge:
T + 5 min 27.7 21.2 6.5 21.2 6.5 j
T + 60 min 1.4 1.2 0.2-1.3 0.1 i
aValues + 0.3 ugCu/L.
bTime zero.
I j
ASV data is difficult to interpret because of the complexity of reactions in the solution and at the electrodes. The ASV signals are pH-dependent, and the area and shape of the peak depend also on the -types and kinds of organic ligands present (Brezonik et al., 1976). A known problem is sorption of' j
_ organic ligands onto the electrode, which affects the signal generated. We have noted both a shiftingLto a more negative potential _ and a broadening of i
the peak in the presence of organic ligands.
These limitations in data interpretation should be considered when data colleci.ed from different sites and generated in different laboratories are compared.
Some information on chemical forms of copper in the soluble fraction of seawater is available in the literature (Table 7). Labile and bound copper concentrations in water samples collected from Saanich Inlet, British Columbia, showed.'large differences with depth.
(See'Sugai and Healy, 1978).
Total copper ranged from 1 to 14 ug/L-with " to 100% of the copper strongly bound to ligands that released the metal or.y on acidification of the water to pH 2.
4 24
Data on tha cupric ion activity in surface and d:ep waters of the Southern California Bight (Williams and Baldwin, 1976) suggest that, in surface waters unaffected by large inputs of copper, the cupric ion activity is controlled primarily by metal-inorganic anion complexes and secondarily, by metal-organic ligand complexes, whereas in polluted waters, copper complexation with organic matter appears to be the major mechanism controlling cupric ion activity. This is supported by Nissenbaum et a_1_. (1972), who report that, in interstitial waters of a reducing marine fjord, polymerized organic matter accounts for about half the total dissolved organic metal complexes, particu-larly of copper, iron, and zinc.
In addition to the actual measurements of labile and bound species in water, concentrations of trace metal species have been calculated froin equili-brium chemical models. These models calculate the way in which specified amounts of metals and ligands are partitioned by all competing reactions in the solution and solid phases. Rect.ntly the more than one dozen available computerized models for equilibrium calculations in aqueous systems were compared (Nordstrom et d., 1979). Consistency among programs was evaluated by comparing the log of the molar concentrations of free ions and complexes for two test solutions:
a hypothetical seawater analysis and a hypothetical river water analysis. The authors propose that the lack of agreement for minor species in seawater reflects primarily differences in the thermodynamic data base of each chemical model, although other f actors such as activity-coefficient calculations, redox ascumptions, temperature corrections, alkalin-ity corrections, and the number of complexes used also may affect the results.
Schmidt (1978) recently reviewed information on the percentage distribution of dissolved species of copper in seawater from predictive models. He considered the models of Zirino and Yamamoto (1972), Florence and Batley (1976), and Kester g a_1_. (1975). Most models indicate the predominant species of Cu are Cu(OH)2 orCu(OH)C1,andCuC0. Uncomplexed Cu+2 and 3
Cu0H+ account for only about 1% of the total at pH 8.1 (Zirino and Yamamoto, 1972). The lack of agreement in percentages calculated for Cu species with different models is probably due to the same reasons proposed by Nordstrom et_
a_1. (1979) for minor species in genera'l (see above). Many of the models do not include interactions with organic ligands. Others suffer from the omission of polynuclear and mixed ligand complexes (Schmidt,1978). When more 25
TABLE 7.
Ccnctntrations of labile and bound species of copper (pg/ liter) measured in seawater collected at different locations.
Labile Bound Method Location Depth Reference m
0.32 8.3 ASVa Scanich Inlet, O
Sugai and Healy (1978) b British Columbia nd 6.7 ASV 5
(bottom, anoxic) 3.7 10.
ASV 10 nd 1.3 ASV 25 0.32 4.8 ASV 60 nd 1.4 ASV 221 nd 3.1 ASV Saanich Inlet, 0
nd 1.3 ASV British Columbia 5
(bottom; nd nd ASV reoxygenated) 160 nd 1.0 ASV 190 4-12.3 Cc Northeast Atlantic Riley and Taylor (1972) d 3+0.3 0.19+
O Narragansett Bay, Duce el al. (197?.)
0.10 R.I.
2.41 0.45 0
Menai Straits, Surface Foster and Morris (0.83-(0.22-N. Wales
[1971) 3.20) 0.78) 0-8.7 2.1-10.2 0
Intake, Unit 1 Surface Alexander (1973)
Northport Power Station, N.Y.
0-8.0 4.2-13.3 0
Effluent; Unit 1 Surface Alexander (1973)
,Northport Power Station, N.Y.
26
Table 7. (cont.) Concentrations of labile and bound species of copper (pg/ liter) measured in seawater collected at different locations.
Labile Bound Method Location Depth Reference m
6-8 16.4-20.4 0 Intake, Unit 2 Surface Alexander (1973)
Northport Power Station, N.Y.
6-13 5.3-22.4 0
Effluent, Unit 2 Surface Alexander (1973)
Northport Power Station, NY 3-5 0-6.2 0
Intake, Unit 3 Surface Alexander (1973)
Northport Power Station, NY 0-19 2.2-9.4 0
Effluent, Unit 3 Surface Alexander (1973)
Northport Power Station, NY aASV, differential pulse anodic stripping voltametry.
bnd, not detected.
cC, Chelex-100 ion exchange resin.
d0, organic extraction of copper chelates.
experiments are performed and the data generated are incorporated into the model. we can expect the predictive capabilities of the model to continue to improve.
APPARENT COMPLEXING CAPACITY The apparent complexing capacity for the receiving waters at both San Onofre and Diablo Canyon Nuclear Power Stations was low, approximately 1 pg Cu/L (Table 8). A typical voltammogram shows the peak area to increase with increased quantities of labile copper in the water (Fig. 5). On a plot 2
of peak area versus Cu + added, the intercept at zero peak area was taken to 27
be the complexing capacity. Any additional copper simply resulted in an increase in peak area corresponding to uncomplexed copper (Fig. 6).
The impact on ecosystems of adding copper to power station effluents is related to the concentratica in the water of ligands that bind copper tiShtly.
If, in the influent water, the ligand concentration is considerably higher than that of the copper, the ligand is available to react with the added copper, and this results in a change in chemical form. Formation of tightly associated copper-ligand complexes results in a form of copper in the effluent that is less toxic to biota and that has a lower affinity to suspended matter.
However, because the apparent complexing capacity that we observed is low, it can be expected that any labile copper added to the effluent waters at San Onofre ar.d Diablo Canyon will remain primarily as such and be in the chemical form considered to be most toxic to the biota.
The concentrations of soluble organic carbon in the water ranged from 1.2 to 2.5 mg C/L.
Little relationship exists between the complexing capacity of the water and the soluble organic carbon (Table 8).
It appears that a signi-ficant fraction of the soluble organic matter is not active in copper complexation.
The apparent complexing capacity was determined on samples that had equilibrated overnight with added copper. Complexation reactions of most of the inorganic metal ligand systems generally reach equilibrium quite rapidly.
On the other hand, copper complexation to high molecular weight humic matter, polynuclear formation, and slow substitution reactions take longer (Chau e_t_
al., 1974 ). The rate of reaction is related to its structure. Chau et jQ.
(1974) report that a 2-h equilibration time was sufficient for copper to complex with EDTA in lake water. We found no significant change in apparent complexing capacity in samples that had equilibrated 12 and 24 h.
This suggests that the quantity of ligand requiring long equilibration time (>24 h) is small and would not change greatly the values obtained.
The final distribution of the copper increment added to each aliquot of water for determining complexing capacity is a function of (1) the amount of copper added, (2) the concentration of other inorganic constituents, and (3) the kinds and amounts of organic ligands present. The added copper may be taken up by labile or nonlabile ligands (Cu + L = Cul), may displace other metals from complexes (Cu + ML = cul + M), or may simply increase the amount of labile copper already present.
28
TABLE 8.
Apparcrit complexing capacity of waters collected in the 1
vicinity of the San Onofre and Diablo Canyon Nuclear Power Stations.
I Sample Date Soluble organic Complexing collected carbon, mg C/L capacity, ug Cu/L Diablo Canyon Discharge 8/11/77 2.0 0.8 Discharge 10/11/77 1.8 1.0 Intake 2.1 0.2 San Onofre Outfall 7/21/77 1.6 0.9 Control 1.4 0.6 Outfall 10/18/77 1.6 0.8 Intake 2.5 0.6 Control 1.4 1.3 Outfall 1/9/78 1.5 0.2 Intake 1.5 0.2 Control 1.2 The complexing capacity technique we used is a procedure for measuring I
the concentration of strong copper-binding ligands in natural seawater. The value obtained does not include the ligands already bound to copper, but only those available for binding or those that the added copper displaces. To obtain a better indication of the concentration of ligands that binds copper strongly, the concentration of bound copper in the water should be added to the value of complexing capacity.
29
f Cu E
$3 s
ai a
Pb E73 I
Applied potential, mV Fig. 5.
Voltamograms obtained with aliquots of sample water to which increasing amounts of copper were added.
3 i
i l
2 e
M
- o0 1 - Complexing capacity d
O"""
O 2
4 6
8 10 Cu" spike, pg/L FIG. 6.
Diagramatic representation of apparent complexing capacity.
30
ULTRAFILTRATION A better assessment of the quantities of the different chemical forms of copper that are present in seawater is possible if data are available on the percentage of copper present in specific molecular weight fractions. We used ultrafiltration techniques to study the molecular weight fractions of copper in seawater. Smith (1976) has used ultrafiltration to study the complexing characteristics of various molecular weight fractions. Organic carbon compounds in seawater have been characterized according to molecular weight fractions by ultrafiltration by Sharp (1973), Maurer (1971), and Ogura (1974, 1977).
64 Seawater samples spiked with high specific activity Cu were ultrafil-64 tered. The availability of the Cu sorbed on the walls and membrane for distribution between the filtrate and the solution remaining in the ultrafiltration cell is uncertain. Therefore, we calculated the percentage in each molecular weight fraction in two ways:
(1) by assuming that the available counts were those in the filtrate and those in the solution remaining in the cell only, and (2) by assuming that the available counts were those that were recovered from all parts of the ultrafiltration system. Table 9 presents the results from the ultrafiltration of seawater samples from San 64 Onofre and Diablo Canyon, assuming unavailability of Cu sorbed on the walls and membrane. Table 10 presents the results based on the assumption of 64 availability of all Cu recovered. Comparing the data in Tables 9 and 10 shows that the agreement is better for the untreated than for the UV-treated 64 water. This is expected because more Cu is sorbed on the walls and membrane after the organic matter is destroyed by UV treatment.
64 The percentage of Cu in each molecular weight fraction differeu greatly with the sample.
In almost all untreated samples, the percentage found in the < 1,000 weight fraction was less than 20. The percentage of 64Cu in the various weight fractions changed substantially with UV treatment. Important results of the UV treatment are as follows:
64 (1) the percentage of Cu in the small molecular weight fraction
(<1,000,) increased.
(2) the percentage in the high' molecular weight fraction (>10,000) increased in most tests.
l 31 l
64 TABLE 9.
Percentage of Cu in molecular weight fractions in ultrafiltered seawater.a Collection Collection UV Molecular weight fractions date site treatment,
>1,000
<10,000 h
<1,000
<10,000 <100,000 >100,000 A.
San Onofre Nuclear Power Station D
May 5, 1977 Discharge 0
45 0
14 41 2
69 0
11 20 July 21, 1977 Discharge 0
18 14 47 21 2
47 10 37 6
October 18, 1977 Discharge 0
16 49 25 10 4
39 25 0
36 Intake 0
14 56 17 13 January 9, 1978 Discharge 0
34 34 14 18 4
36 35 0
29 B.
Diablo Canyon Nuclear Power Station June 7, 1977 Discharge 0
19 23 29 29 2
51 1
19 29 August 11, 1977 Discharge 0
12 21 48 19 4
18 22 17 43 October 11, 1977 Discharge 0
14 20 47 19 4
43 18 0
39 aCalculations based on assumption that the 64 u sorbed on the walls and C
membrane were unavailable for filtration.
bData are suspect because filters were not washed as well as for subsequent experiments and glycerin used by the manufacturer in preparation of membranes may not have been completely removed.
32
64 TABLE 10. Percentage of Cu in molecular weight fractions in ultrafiltered seawater.a 4
i Collection Collection UV Molecular-weight fractions date site treatment,
>1,000
>10,000 h
<1,000 <10,000 <100,000 >100,000 A.
San Onofre Nuclear Power Station b
May 5,1977 Discharge 0
37 0
11 34 2
53 0
9 15 >
July 21, 1977 Discharge 0
12 9
31 14 2
30 6
23 4
I October 18, 1977 Discharge 0
11 41 20 8
4 18 11 0
16 Intake 0
11 44 14 10 January 9, 1978 Discharge 0
26 26 11 14 4
19 18 0
15 B.
Diablo Canyon Nuclear Power Station June 7, 1977 Discharge 0
13 16 20 20 2
27 1
10 16 August 11, 1977 Discharge 0
9 16 35 14 4
9 11 9
22 October 11, 1977 Discharps 0
10 15 35 14 4
23 10 0
21 aCalculations were based on the assumption that the 64 u sorbed on the C
walls and membrane were available for filtration.
b ata are suspect because filters were not washed as well as for subsequent D
experiments and glycerin used by the manufactures in preparing membranes may not have been completely removed.
- 1 33
i (3) the percentage in the intermediate fractions (>1,000 <100,000) decreased in nearly all cases.
(4) the percentage sorbed on the walls and membrane increased; the 64 greater increase was in the amount of Cu sorbed on the walls (acid wash).
Because UV treatment destroys organic matter in the water, it is assumed that the organic-Cu complexes occur in the intermediate molecular weight 64 fraction, which contained less Cu after oxidation. Both the small
(<1,000) and high molecular weight (>100,000) soluble fractions increased after UV oxidation as did the fraction sorbed on both the membrane and assembly walls.
Increases in these fractions indicate changes in physicochemical forms of the copper when the organic matter, which contains important binding sites, has been removed. The copper freed from the organic matter appeared either in the small molecular weight fraction consisting most likely of free ions, ion pairs, cnd small inorganic complexes (<l,000), or in the large molecular weight fraction (>100,000). The increase in the sorbed fraction on the walls and membrane may be from both of these fractions. The smaller molecular weight fraction appears very reactive chemically and sorbs readily on the assembly walls and surface of the membrane.
Some of the large inorganic complexes may also be retained in the pores of the membrane.
An indication of the amount of copper in the intermediate molecular weight fraction (>1,000 <100,000) that is associated with organic matter can 64 be obtained by comparing the total percentage of Cu in this weight fraction before end after UV treatment. Let us assume that the percentage of 64Cu remaining in the intermediate weight fraction af ter UV treatment represents the inorganic-bound copper and that the difference in the 64 percentage of Cu in this weight fraction before ard after treatment represents the organic-bound copper. The data indicate that the percentage of 64 the Cu distributed in the intermediate weight fraction that was associated with organic matter varied greatly with the sample (Table 11). Note that the calculated percentage of organic and inorganic bound copper are approximate 64 values because more Cu is bound to the walls and membrane of the ultrafiltration system after UV treatment.
64 Recovery of Cu added to the seawater samples initially ranged between 85 and 101%; x = 95.0 1 6.1 in the untreated water and 92.2 1 9.4 for the 34
0 TABLE 11. Percentagn of inorganic and organic bound Cu in the intermediate molecular weight fraction (>l,000 <100,000 molecular weight) of discharge water.
Col.
Col.
Assumption of unavailibility* Assumption of availability date site Inorganic Organic-OrgangCuTotalInorganigCu bound band 6 bound 64Cu Total bound 64Cu 6/7/77 Diablo Canyon 20 32 52 11 25 36 7/21/77 San Onofre 47 14 61 29 11 40 8/11/77 Diablo Canyon 39 30 69 20 31 51 10/11/77 Diablo Canyon 18 49 67 10 40 50 10/18/77 San Onofre 25 51 76 11 50 61 7
1/9/78 San Onofre 35 13 48 18 19 37 abased on the assumption that the 64Cu sorbed on the walls and membrane of the ultrafiltration chamber were unavailable for filtration.
b ased on the assumption that the 64Cu sorbed on the walls and membrane of 8
the ultrafiltration chamber were available for filtration.
04 UV-treated water. The final distribution of the Cu spike added to each water sample differed with the water and treatment. The percentage of the 64Cu in the dissolved fraction (filtrate and the solution remaining in the ultrafiltration cell) of untreated water was 78 1 4, and in UV-treated water was 55 1 5 (see Table 12). The percentages associated with the membranes were variable and showed no consistent pattern with pore size. The percentage of 64Cu removed from the appparatus by the acid rinse was variable also. The average percentage recovered by the acid was 18 for the 1,000 molecular-weight cut-off membrane (MWM) and 11 for the 10,000 and 100,000 W M.
The larger percentage recovered on the 1,000 MWM may be related to the longer time required for filtering through the membrane with the smaller pores; about 2 h were required for the 120 mi to filter through the 1,000 MWM, whereas only 0.5 h was required for the 10,000 and 100,000 W M.
The copper in the >100,000 molecular weight fraction may exist in a l
number of forms. A reaction that may occur is the sorption of copper to colloidal phases of other metals. Jackson and Morgan (1978) have discussed i
35
~ -. _
0 TABLE 12. Percentage of Cu recovered in the dissolved (filtrate plus the solution in the ultrafiltration cell) and sorbed (to the walls and membrane) fractions of the ultrafiltration system.
UV Dissolved Collection Collection treatment, fraction.
Sorbed fraction date site h
total Membrane
. Walls Total A.
San Onofre Nuclear Power Station May 5,1977 Discharge 0
82 7
11 18 2
77 8
15 23 July 21,1977 Discharge 0
66 25 9
34 j
2 63 18 19 37 October 18, 1977 Discharge 0
81 7
12 19 4
45 15 40 55 I
Intake 0
79 7
14 21 r
January 9, 1978 Discharge 0
77 10 13 23 4
52 13 35 48 1
B.
Diablo Canyon Nuclear Power Station June 7,1977 Discharge 0
70 14 16 30 2
54 14 32 46 August 11, 1977 Discharge 0
74 20 6
26 4
50 24 26 50 October 11, 1977 Discharge 0
74 10 16 26 4
53 16 30 46 J
b i
4 36 1
.,-,r,
,,-,.n-c,
,s.,
w n
,u.,
{
.the adsorption of metal ions to Fe(OH)3(s), or Fe00H(s), or other solid pha',es of iron. Iron oxide may have a negative surface charge in seawater, thes creating a favorable electrostatic condition for adsorption of cations or su'*f ace complexation with -OH groups. Destruction of the dissolved organic material with UV treatment probably results in the release of copper in the i
form that would be available for adsorption to the surface of inorganic colloids.
j Most researchars agree that organic ligands form complexes and chelates with copper that affect transport and availability in natural waters (Jenne, 1%8; Rashid and Leonard,1973; Guy et al.,1975). Two mechanisms by which organic compounds.can solubilize metals are (1) by forming metal-ligand complexes with sorption characteristics different from those of the free metal ion or (2) by solubilizing the iron and manganese oxides and thus releasing sorbed trace metals (Guy et al.,1975). An important group of dissolved organic material is humic substances.
It includes refractory organic molecules that comprise approximately 90% of the dissolved organic material in seawater.
Humic substances are classified by solubility, and the two classes most L
i often referred to are: humic acid, which is soluble in base and insoluble in l
acid, and fulvic acid, which is soluble in both acid and base. The molecules consist of long carbon chains, complex aromatic structures (Cline,1974), and I
functional groups containing oxygen, nitrogen, sulphur, and phosphorus, such as the-aromatic amine (-N:) and carboxylate ('CO-) groups. Humic substances l
may scavenge copper ions and thus play a major role in its physicochemical transformation.
Several researchers have investigated the molecular weight fractions of l
aquatic humus by ultrafiltration (Gjessing, 1973; Giesy and Briese, 1977.
Allen (1976) studied some of the ecological implications of dissolved organic matter after fractionating lake water into molecular. weight compartments.
Giesy and associates (1977) have extensively studied various metal I
associations of naturally occurring aquatic organic fractions. Smith (1976) determined the copper-complexation capacities of various molecular weight l
fractions of dissolved organic matter. in estuarine waters by a combination of l
ultrafiltration and anodic stripping. voltammetry techniques.
(
Some researchers have used ultrafiltration as a sequential filtration process, where the filtrate that passes the largest pore-size membrane is then 37 m
filtered through the next smaller pore size, and so on to the smallest (Giesy, 1977, Blatt et al.,1967; and Smith,1976).
Our research has identified at least two disadvantages of this process:
(1) sequential filtration may remove a very significant amount of the metals or metal complexes from the solution through sorption onto the membranes and walls, (2) reducing the volume of solution above the membrane to less than 10-20% of the original volume produces a sharp increase in the concentrations of metals in the filtrate, which may result from a shift in the equilibrium of the reaction. However, this sorption ento the membrane and walls and change in concentration with the sample volume filtered can be minimized if aliquots of the original solution are filtered in parallel ising multiple filtration setups, each with a different pore-size membrane. Then only one membrane sorption effect need be considered for each filtration, instead of the three or four in sequential series. To obtain more ideal fractionating conditions, the solution should not be concentrated on the membrar,e. By filtering the solution through the membrane under positive N2 pressure to 50% of the original volume, abrupt changes in concentration are avoided, and both the filtrate and the solution remaining in the ultrafiltration cell can be collected and analyzed against the control solution.
The presence of significant amounts of dissolved, organically associated copper in seawater has been demonstrated previously. Slowey, Jeffrey, and Hood (1967) demonstrated that a fraction (8 to 50%) of the total dissolved copper in a number of seawater samples from the Gulf of Mexico could be extracted directly in a nonpolar solvent. Foster and Morris (1971) reported organic bound copper varied from 6 to (0% of the total. Further tre, increased concentrations of ionic copper are usually obtained in filtered seawater samples that have been oxidized to destroy the dissolved organic matter (Corcoran and Alexander,1964; Slowey et al.,1967; Williams,1969; Williams and Baldwin, 1976).
The source and nature of the organic matter associated with the copper are as yet unresolved. Organic compounds may be excreted by marine organisms, may arise from the decomposition of dead organisms, or may be introduced in fresh water runoff. Foster and Morris (1971) suggest that concentrations or organic bound copper in seawater at least partially result from active marine production of organic matter. The annual variation of dissolved organic 38
carbon (DOC) was determined by Foster and Morris (1971). Concentrations were elevated during the spring and summer months. The maximum value was detected in autumn, thence followed a sharp drop to minimum concentrations between December and February. In water from both Diablo Canyon and San Onofre the largest percentages of organic bound copper were detected in October. More data are needed to establish conclusively a seasonal trend. Foster and Morris (1971) determined the concentrations of DOC, ionic copper, and organic bound copper (total less ionic) in a series of water samples collected in the Menai Straits. They detected no direct correspendence with DOC and organic bound copper.
l i
1 t
l l
l l
39 i
m m
~.
CONCLUSIONS The results of our study of copper in waters near the San Onofre and Diablo Canyon Nuclear Power Stations indicate that the impact on marine environments of using copper alloys in condenser tubing of power stations depends on the operating conditions at the site and the composition of the coolant waters. The operating conditions affect the quantities of copper releaseo and the composition of the water affects the physicochemical forms of copper in the water.
i We expect little or no effect on marine biota when these stations are operating normally, i.e., when large volumes of surf ace, open ocean waters circulate continuously through the condensers. At both stations the intake waters were low in copper, dissolved organic carbon, and suspended particles.
Differences in copper concentration between intake and discharge waters were small or undetectable.
The physicochemical forms of copper in the effluent were evaluated using three different techniques. All of our data indicate that the concentrations of labile copper, the form toxic to most biota, are low; the concentration of Chelex-100-labile copper was generally <0.5 pg Cu/L, that of ASV-labile copper was at or below detection limits (@,3 pg/L), and 20%
of the copper was in the <1000 molecular-weight fraction. Data available (Harrison,1980b) indicate that significant mortalities of marine biota do i
not occur in waters containing concentrations of labile copper <1 pg/L.
Effects on marine biota from increased copper concentrations in the effluent are expected following start-up of water circulating though large copper-alloy condensers after an enforced shutdown.
The impact will be l
determined by the maximum concentration and duration of the copper pulse and on the number of copper-sensitive organisms in the discharge zone.
l Our results obtained during the start-up at Diablo Canyon indicate that I
a large fraction of the copper discharged during start-up was labile.
Because, during this start-up, the maximum concentration of labile copper was only 21 pg/L and the duration was short, the number of organisms that 40 l
A M
Gay have been affected by this release was most likely small, and the impact was probably of little consequence. However, when large amounts of copper alloy tubing are present and the tubing is drained at shutdown, the copper pulse is high in concentration and extended in duration (Warrick et al.,
1975). Under these circumstances, some biota may die or exhibit sublethal effects. Such effects could be minimized if, after shutdown of the reactor, water was circulated continuously through the cooling system or if, during start-up, natural organic chelators were added to the water to reduce the concentration of labile copper.
i I
d j
41 i
a
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48
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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 (1978).
W. G. Sunda and R. R. L. Guillard, "The Relationship Between Cupric Ion Activity and the Toxicity of Copper to Phytoplankton," J. Mar. Res.
4, 511 (1976).
W. G. Sunda and J. A. Lewis, " Effects of Complexation by Natural Organic Ligands on the Toxicity of Copper to a Unicellular Algae Monochrysis lutheri,"
Limnol. Oceanogr. 23, 870, 1978, W. G. Sunda and P. A. Gillespie, "The Response of a Marine Bacterlun to Cupric Ion and Its Use to Estimate Cupric Ion Activity in Seawater,"
J. Mar. Res.
37,, 761 (1979).
49
J. W. Warrick, S. G. Sharp, and S. J. Friedrick, Chemical, Biological, and Corrosion Investigations Related to the Testing of the Diablo Canyon Unit 1 Cooling Water System, Pacific Gas and Electric, Dept. of Eng. Research, San Ramon, CA, Report No. 7333, 129 (1975).
P. M. Williams, "The Association of Copper with Dissolved Organic Matter in Seawater," Limnol. Oceanogr _14,156 (1969).
P. M. Williams and R. J. Baldwin, " Cupric Iori Activity in Coastal Seawater,"
Mar. Sci. Consnun. 2, 161 (1976).
D. R. Young, Tsu-Kai Jan, and M. D. Moore, " Metals in Power Plant Cooling Water Discharges," Coastal Water Research Project Annual Report (1977).
D. R. Young, T. Jan, and T. C. Heesen, " Cycling of Trace Metal and Chlorinated Hydrocarbon Wastes in the Southern California Bight" in Proc. Fourth Biennial International Estuarine Research conference, Mt. Pocano, PA,1977.
A. Zirino and S. Yamamoto, "A pH-Dependent Model for the Chemical Speciation of Copper, Zinc, Cadmium, and.ead in Seawater," Limnol. Oceanogr. 17, 661 (1972).
i l
BSS/cg l
l
[
j 50
i GLOSSARY Bound copper species:
include stable copper-organic complexes, copper bound to high molecular weight organic matter, some inorganic complexes, and occluded in or sorbed lightly on highly dispersed colloids. Another name given members of this group of species is nonlabile copper.
Chemical species:
refers to the actual form in which a molecule or ion is present in solution.
Labile copper species:
include ions, ion pairs, readily dissociable (hbile) inorganic and organic complexes, and easily exchangeable copper sorbed on either colloidal inorganic or organic matter. Another name given this group of species is f ree copper.
Mettl sinks on particles:
represent different solid forms of metals on particles, such as sulfides, carbonates, e.tc.
Particulate fraction of water:
that which is retained by a 0.4-or a 0.45-m filter.
Soluble fraction of water:
that which passes through a 0.4-or a 0.45-m filter.
I Southern California Bight:
the area of California coastline south of Point Conception.
i l
51
APPENDIX A PROCEDURE FOR CLEANING SAMPLE CONTAINERS CONTAINERS OF <10pg Cu/L SAMPLES New Polypropylene containers were filled with reagent-grade, concentrated HNO3 and stored at room temperature for at least 7 da to leach out metal contaminants. The acid was then removed, and the containers rinsed five times with doubly distilled (glass) water (DDW) and filled with 0.05% Ultrex HNO 3
i in DDW. Af ter at least 4 da, the dilute acid was discarded, and the containers were rinsed five times with DDU and then stored and filled with DDW until use.
CONTAINERS OF >1099 Cu/L SAMPLES New Polypropylene containers were soaked for at least 2 da in a 2% MICR0 bath. The cor. tainers were removed from the bath, rinsed five times with DDW, drained, and stored in sealed plastic bags until use.
l 53 i
APPENDIX B CALCULATION OF MOLECULAR WEIGHT FRACTIONS OF COPPER IN SEAWATER 64 The first step calculating the ultrafiltration data corrects the Cu activity in the sample for background counts and for decay to time zero.
64 Next, the corrected Cu activity in each sample is converted to the percentage of the total activity present in the initial solution before the ultrafiltration process is initiated. This calculation permits the data from 64 different experiments to be compared even though the Cu spike is not exactly the same in each experiment. The spiked seawater is ultrafiltered through each molecular weight cutoff membrane in duplicate.
Generally good agreement between duplicate samples was obtained (Tables 64 B-1 through B-7).
The percentage of the Cu in each of the three 40-ml aliquots of filtrate collected (F, F, F ) generally increased slightly 1
2 3
with increased volume of sample filtered. After examining the data on the 64 percentage of Cu '.n the aliquots of the filtrate, we selected a representative vali e that was either the value from the second 40-mi sliquot or the average of all 40-m1 aliquots.
In prelimiaary experiments, we sampled filtrates serially during the ultrafiltration of entire sample volunes. The following pattern of change in 64Cu concettration was determined: the concentration was generally low in the aliquots collected during the filtration of the first 5 to 10% of the sample volune, changed little or increased slightly during the filtration of r
the next 80%, and then increased abruptly during the filtration of the last 10 20 15%. Because of these changes, we adop+ed the procedure of taking 10-ml aliquots from each 40-ml of filtrate that passed through the iaembrane to monitor changes in concentration with sample volume, and stopped filtering when half the sample volume was filtered to avoid the rapid changes in concentration with reduced volume of the solution remaining in the ultrafiltration cell. We postulate that the lower levels of activity in the 64 initial samples result from sorption of Cu onto the filter (Table B-1) and 55
3 64 TABLE B-1.. Percentage of Cu recovered in the different components of the system after ultrafiltration of seawater through 0.4-um pre filters (San Onofre, 10/18/77).
Stated UV Retained Acid mol wt cutoff treatment F i (2
F F total solution Filter wash recovered
- 3 h
40 ml 40 ml 40 ml 120 ml ~
.120 ml l
1000 0
1.4 1.6 2.3 5.3 63.3 ^
2.8 24.9 96.3 0
2.1 2.2 3.6 769 70.1 3.6 13.1 94.7
.Y = 1.7 1.9b 3.0
' 6.6 66.7 3.2 19.0 95.5 10,000 0
7.2 7.5 7.9 22.6 55.0 8.9 8.8 9".3 0
8.4 -
9.6 11.4
.29.4 54.8 9.6 10.0
.8 Y = 7.8 8.6b 9.7 26.0 53.9 9.25 9.4 38.55 100,000 0
10.7 13.6 12.6.
36.9 47.8 7.9
.9.0 101.6 0
10.7 11.0 12.9 34.6 45.3 9.3 7.4 96.6 ui I = 10.7 12.3b
-12.8
~ 35.8 46.6 8.6 8.2 99.1 cn 1000-4-
2.0 1.6 2.3 5.9 20.8 8.4 54.8 89.9 4
0.4 1.5 1.4 3.3 19.7 5.'3 59.2 87.5 Y=i.2' 1.6b 1.8 4.6 20.2 6.85 57.0' 88.7 10,000 4
5.1 7.9 9.1 22.1 41.4 13.0 25.1 101.6 4
5.5 9.0 8.2 22.7 46.5 12.2 23.8 105.2 I = 5.3 8.5 8.6 22.4 44.0-12.6 24.45 103.4 7.5b 100,000 4
3.6 3.0 4.5 11.1 25.2 27.5 37.1 100.9 4
4.4 6.8 3.2 14.4 35.8 23.7 39.3 113.2 Y = 4.0 4.9 3.8 12.8 30.5-25.6 38.2 106.95
'4.3b aF, F2, and F3 are the three 40-m1 aliquots of filtrate, respectively.
1 bValue of the filtrate used in' the calculation of G, the percentage greater than the molecular weight cutoff of the membrane.
f
04 TABLE B-2.
Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-um filtered seawater (Diablo Canyon, 6/7/77).
Stated UV Retained Acid mol wt cutoff treatment F
F f
I F total solution Filter wash recovered 1
2 3
4 h
30 ml 30 ml 30 ml 30 ml 120 ml 120 mlb b
1000 0
2.4 16.4 50.8C 7.5 77.1 5.0 48.4 16.7 16.6 86.7 O
Y=
1.25 d 5.0 48.4 16.7 16.6 86.7 10.000 0
12.8 57.4 10.8 13.6 94.6 0
16.9 54.8 10.9 18.1 100.7 I=
3.72 d 14.9 56.1 10.85 15.9 97.65 100,000 0
25.5 41.5 14_1 14.9 96.0 0
16.9 34.9 16.2 17.7 85.7 i=
5.3 d 21.2 38.2 15.2 16.3 90.85 m
u 1000 2
1.1 1.8 2.3 2.8 8.0 33.6 21.6 30.7 93.9 2
14.7 32.0 16.1 35.2 98.6 Y=
2.85 d 11.4 32.9 18.9 33.0 96.25 10,000 2
1.9 2.7 3.5 3.3 11.4 32.5 11.2 33.3 88.4 2
11.5 32.9 12.9 36.4 93.7 Y=
2.86 d 11.45 32.7 12.05 34.9 91.05 100,000 2
2.7 3.3 3.3 3.2 12.5 29.6 13.7 33.7 89.5 2
16.3 23.1 10.1 23.4 72.9 Y=
3.6 d 14.4 26.3 11.9 28.6 81.2 ap1. F, F, and F4 are the four 30-ml serial samples of filtrates.
2 3 b n aliquot of the filtrate was taken for counting only after the entire 120 ml was collected.
A cThe filter value was excessively high; possibly due to filter insufficiently cleaned of glycerin coating.
These data were not used, dValue of the filtrate used in the calculation of the percentage of the 64Cu that was greater than the molecular weight cutofn 'f the membrane;.the total percentage in the filtrate was divided by four.
5.
64
' TABLE B-3.
Percentage of Cu recovered in the different components of the system after ultrafiltration of seawater through 0.4-pm filtered seawater (San Onofre, 7/21/77).
. Stated UV Retained Acid 5
mol wt cutoff. treatment
.F 1 F
3 4
F total solution. Filter wash. recovered 2
F F
h 30 ml : 30 ml -
30 ml-30 ml 120 ml 120 alb 1000 0
2.3 0.6 0.1 0.0 3.0 21.7 53.0 4.7 82.4 0
0.6 0.3 0.0 0.0.
0.9 18.6 55.6 4.2 79.3 Y = 1.45 0.45
-0.05 0.0 1.95 20.15 54.3 4.45 80.9
' 0.5 d
~
110,000 0
2.4 2.3 3.3 3.3 11.3 68.9 11.2 10.5 101.9
.0 3.0 3.3 3.2 3.7 13.2 63.4 9.3 11.8 97.7
'li = 2.7 2.8
.3.25 3.5 12.25 "
66.15 10.25 11.15 99.8 3.1 d 100,000 0
6.2 6.1 7.0
- 6.3 25.6 41.4 3.8 11.1 81.9 O
7.2b 6.'1b-26.6 37.5 18.2 9.2 91.5
- 4 7=
6.5 d 26.1 39.45 11.0
'10.15 86.7 L
co 1000 -
2 2.5 0.6 0.C 0.3 3.4 9.0 53.0c
- 8.3 73.7 2
1.8 1.8 1.7 1.7 6.8 22.1 22.6 18.2 69.7 x
1.7 d 6.8 22.1 22.6 18.2 71.7 10,000
- 2 2.2 2.0 2.3 1.4
' 7.9 30.1 28.1 27.4 93.5
~ "
2' 4.2 0.8 3.5 5.3 ~
13.8 23.8 11.6 13.3 62.5 T = 3.2 1.4-2.9
'3.35 10.85 26.95 19.85 20.35
'78.0 2.7 d 100,000 2
' 9.2b 3.6b 25.6 29.5 6.7 17.6 79.4 2-12.1
' 2.3 '
-4.4 3.6 22.4 24.2 19.3 16.0 81.9 I=.
6.0 d-24.0 26.85 13.0 16.8 80.65-aF, F, F3 F4 are the four 30-m1 aliquots of filtrate.
1 2 bThese filtrates are two 60-m1 aliquots.
cThis filter value was excessively high, possibly due to filter insufficiently cleaned of glycerin coating.
These data were not used.
-dValue of the filtrate used in the calculation'of G, the percentage greater than the molecular weight cutoff of the membrane; the total percentage.in the filtrate was divided by four.
C'
TABLE B-4.
Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-um filtered seawater (Diablo Canyon, 8/11/77).
S'ated UV Retained Acid t
mol wt cutoff t,reatment F
F f
F F total solution Filter wash recovered 1
2 3
4
.h 30 ml 30 ml 30 ml 30 ml 120 ml 120 mlb 1000 0
0.5 0.7 0.9 1.1 3.2 54.3 26.3 9.5 93.3 0
0.5 0.7 0.5 0.5 2.3 32.2 45.5 4.8 84.8 Y = 0.5 0.7 b 0.7 0.8 2.7 43.2 35.9 7.2 89.1 10,000 0
2.1 2.3 2.3 2.6 9.3 71.3 8.2 7.5 96.3 0
4.4 4.5 4.6 4.8 18.3 63.9 9.7 5.4 97.3 x = 3.3 3.4 b 3.5 3.7 13.8 67.6 9.0 6.5 96.8 100,000 0
7.0 6.6 8.2 8.8 30.6 46.8 13.8 5.7 96.9 D
0 8.4c 8.9 34.6 48.9 16.2 4.5 104.2 Y=
8.15 c 32.6 47.9 15.0 5.1 100.55 mu) 1000
-4 0.6 0.6 0.7 1.1 3.0 30.5 22.2 31.9 87.6 4
0.6 0.6 0.8 0.8 2.8 26.8 29.9 27.8 87.3 Y = 0.6 0.6 0.75 0.95 2.9 28.7 26.0 29.9 87.5 0.7 b 10,000 4
1.7 1.5 2.0 1.6 6.8 34.0 26.2 21.5, 88.5 4
1.9 2.3 2.7 3.2 10.1 34.0 22.1 27.3 93.5 I = 1.8 1.9 2.35 2.4 8.45 34.0 24.15 24.4 91.0 2.l b 100,000 4
4.1 3.8 3.5 4.4 15.8 38.5 21.8 22.6 98.7 4
3.4c 4.6C 16.0 41.9 18.6 25.6 102.1 b
15.9 40.2 20.2 24.1 100.4 7=
4.0 aF, F. F, F4 are the four 30-m1 aliquots of filtrate.
1 2 3 b alue of the filtrate used in the calculation of G, the percentage greater than the molecular weight cutoff l
V of the membrane; the total percentage in the filtrate was divided by four.
cThese filtrates are two 60-m1 aliquots.
L_ _
64 TABLE B-5.
Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-pm filtered seawater (Diablo Canyon, 10/12/77).
Stated UV Retained Acid 1
mol wt cutoff treatment F
F f
F total solution Filter wash recovered g
2 3
h 40 ml 40 ml 40 ml 120 ml 120 ml 1000 0
1.5 1.0 1.1 3.6 54.7 3.0 30.3 91.6 0
1.6 2.0 2.6 6.2 73.6 4.4 21.4 105.6 Y = 1.55 1.5 1.85 4.9 64.2 3.7 25.85 98.6 1.6 b 10,000 0
4.3 4.3 4.2 12.8 60.2 7.5 15.9 96.4 0
3.8 4.1 4.5 12.3 61.2 14.8 8.9 97.2 Y = 4.05 4.2 b 4.35 12.55 60 7 11.15 12.4 96.8 100,000 0
9.4 10.1 8.6 28.1 42.9 18.3 10.9 100.2 0
10.6 11.7 10.5 32.7 47.3 12.4 9.9 102.3 g
.Y = 10.0 10.9 9.55 30.4 45.1 15.35 10.4 101.25 10.1 b 1000 4
0.3 1.2 1.6 3.0 25.8 33.3C 30.5 92.6 4
2.5 3.1 3.0 8.5 30.6 8.1 49.1 96.3 Y=
2.8 b 10,000 4
5.6 6.5 7.2 19.3 37.3 14.6 26.9 98.1 4
7.0 7.7 7.6 22.3 43.4 18.1 16.8 100.6 x = 6.3 7.1 7.4 20.8 40.4 16.35 21.85 99.35 6.9 b 100,000 4
2.2 2.7 3.1 8.0 17.7 21.7 17.9 65.3d 4
3.5 3.2 4.7 11.3 30.6 23.8 19.6 85.3 Y=
3.8 b aF, F, and F3 are the three 40-m1 aliquots of filtrate, respectively.
1 2 b alue of the filtrate used in the calculation of G, the percentage greater than the molecular weight V
cutoff of the membrane.
cThis filter value was excessively high, possibly due to filter insufficiently cleaned of glycerin coating.
These data were not used.
.dThe total counts recovered were too low, so none of those data were used, i
64 TABLE B-6.
Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-um filtere.d seawater (San Onofre, (intake) 10/18/77).
Stated UV Retained Acid 1
mol wt cutoff treatment F
F f
F total solution Filter wash recovered y
2 3
h 40 ml
- 40 ml 40 ml 120 ml 120 ml 1000 0
1.2 1.9 2.3 5.4 60.6 4.0 17.5 87.5 0
1.0 -
1.7 1.5 4.2 72.9
- 3. 5, 19.1 99.7 I = 1.1 1.8 1.9 4.8 66.9 3.75 18.3 93.6 1.6 b 10,000 0
10.15 10.7 11.2 32.0 50.8 7.7 10.2 100.75 0
8.8 8.7 9.2 25.7 55.3 7.6 10.7 99.3 I = 9.5 9.7 10.2 28.9 53.1 7.65 10.45 100.0 9.6 b 100,000 0
10.8 12.35 12.1 35.3 40.0 9.4 17.8 102.5 0
11.2 12.3 12.2 35.7 50.9 8.3 8.1 103.0 I = 11.0 12.33 12.5 35.5 45.45 8.9 12.95 102.75 b
11.8 arg, p2 and F3 are the three 40-m1 aliquots of filtrate, b alue of the filtrate used in the calculation of G, the percentage greater than the molecular weight V
cutoff of the membrane.
i 64 TABLE B-7.
Percentage of Cu recovered in the different components of the system after ultrafiltration of 0.4-pm filtered seawater (San Onofre,1/10/78).
Stated UV Retained Acid mol wt cutoff treatment F
F F
F total solution Filter wash recovered i
2 3
h 40 ml 40 ml 40 ml 121 ml 120 ml 1000 0
3.4 4.3 4.7 12.5 58.1 3.9 17.8 92.3 0
2.4 3.6 4.1 10.1 53.9 4.9 22.0 90.9 I = 2.9 3.95 4.4 11.3 56.0 4.4 19.9 91.6 3.8 b 10,000 0
6.8 8.6 9.4 24.9 52.0 10.4 8.4 95.7 0
8.6 10.0 10.4 29.0 52.4 8.9 9.1 99.4 I = 7.7 9.3 9.9 26.95 52.2 9.65 8.75 97.55 9.0 b 100,000 0
9.4 10.6 10.6 30.7 44.0 15.1 8.3 93.1 0
9.3 10.4
.9.6 29.3 43.3 19.2 10.2 102.0 T = 9.35 10.5 10.1 30.0 43.65 17.15 9.25 100.05 N
10.0 b 1000 4
1.9 2.3 2.2 6.5 33.6 7.6 46.0 93.7 4
3.3 2.1 2.6 8.0 30.8 8.2 46.9 93.9 I = 2.6 2.2 2.4 7.25 32.2 7.9 46.45 93.8 2.4 b 10,000 4
6.3 7.3 8.7 22.3 41.4 13.2 25.4 102.3 4
7.6' 9.4 10.2 27.2 43.0 13.0 12.9 96.1 i = 6.95 8.35 9.45 24.75 42.2 13.1 19.15 99.2 8.3 b 100,000 4
5.9 4.5 4.8 15.1 27.5 18.6 40.1 101.3 4
4.2 5.4 3.8 13.4 27.4 19.4 38.3 100.5 I = 5.05 4.95 4.3 14.25 28.45 19.0 39.2 100.0 4.8 b
, af F2 and F3 are the three 40 ml-aliquots of filtrate.
i b alue.of the filtrate used in the calculation of G, the percentage greater than the molecular weight V
cutoff of the membrane.
that the higher levels in the final samples result from dissociation of the copper-ligand complex or desorption from colloidal material.
64 We calculated the percentage of Cu retained by each membrane. This 64 value depends on the amount of Cu associated with molecules larger than the pore size of the membrane. The reaction of copper (Cu) with ligands and other large molecules or aggregates (L) can be expressed as follows:
k g ' Cut.
(1)
Cu + L,
k2 Charges have been eliminated for simplicity. The distribution of copper in the ultrafiltration system can be represented diagrammatically as shown in i
Fig. B-1.
The total copper (Cu ) in the system available for distribution between t
the filtrate and the solution remaining in the cell is:
Cut = CuL + Cu, (2) and the copper associated with ligands is:
Cul = Cut - Cu.
(3)
If the molecular weight of the copper-ligand complex is greater than the molecular weight cutoff of the membrane, it will be retained by the membrane; the solution remaining in the cell would contain Cu + Cul, whereas the filtrate would contain only Cu.
The percentage greater than the molecular weight cutoff of the membrane (G) can be calculated from the relationship:
Cu - Cu ful (100) or (100).
(4) t
%G =
Cu t
t l
l l
l 63 i
4 Pressurized inflow e
e e
8 e
e
.S e
e e
.e c Membrane
/
]
QEQ d
Outflow FIG. B-1.
Amicon ultrafiltration system.
64 4
64 Let us assume that the total activity of Cu in the water at the time it was introduced into the ultrafiltration system was 1000 picocuries (pCi).
Using average values for the duplicates that were obtained when a 1000 molecular weight cutoff membrane was used (Table B-1), we calculate 955 pCi (1000 x 95.5%) to be recovered; 733 pCi of this would be in the filtrate and solution remaining in the cell [1000 x (6.6% + 66.7%)], and 222 pCi on the walls and membrane [1000 x (3.2% + 19.0%)]. There is a question whether the 64Cu sorbed to the walls and membrane is available for distribution between the solution remaining in the cell and the filtrate. Therefore, we calculated the percentage in each molecular weight fraction using a total of 733 pCi (pCi available in filtrate and retentate) and a total of 955 pCi (total pCi recovered).
By performing these two calculations, we determined whether assumptions of availability of the copper affected the interpretation of data.
64 Let us assume first that the Cu sorbed to the walls and membrane were unavailable for distribution between the solution in the cell and filtrate and 64 base our calculations on a total Cu activity of 733 pCi in the 240 ml of 64 sample; a total available Cu concentration of 3.05 pCi/ml.
64 The percentage of Cu in the 40-ml aliquot that we considered to represent the filtrate was 1.9, a concentration of 0.48 pCi/ml (1000
.98)
Using equation (4), the percentage greater than the 1000 molecular weight cutoff membrane (MWM) is
%G = 3.05 -
.48 x 100 = 84.
Calculations Hmilar to those made with the data obtained when a 1000 MWM was used in the apparatus were made also with the data obtained when a 10,000 and 100,000 MWM were used.
The percent retained by each of the membranes decreased with an increase in the molecular weight cutoff (Table B-8).
From the data in TableiB-8 the percent in each molecular weight fraction can be calculated by difference.
For this sample, the percentages are as follows:
>1000 MW = 16 (100-84);
>1,000 <10,000 MW = 50 (84-34), >10,000 <100,000 MW = 25 (34-9);
>100,000 MW = 9.
65 i
m
64 TABLE B-8.
Percentage of Cu recove*cd in the different components of the system af ter ultrafiltration of seawater through 0.4-tm pore filters (SanOnofre, 10/18/77).
a 64 64 b c
Mol wt cutoff Assumption Total Cu Filtrate Cu Percent G 1,000 I
3.05 0.48 84 II 3.98 0.48 88 10,000 I
3.28 2.15 34 II 4.11 2.15 48 100,000 I
3.40 3.08 9
II 4.13 3.08 25 aAssumption I:
the 64Cu sorbed on the walls and membrane were not available for distribugjCu sorbed on the walls and membrane were available on between the filtrate and retentate.
Assumption II:
the for distribution between the filtrate and retentate.
b oncentration of 64 u in representative filtrate.
C C
cG = percentage greater than molecular weight cutoff of the membrane.
Let us assume next that all the 64Cu recovered is available. This is equivalent to 955 pCi in the 240-ml sample, or 3.98 pCi/ml. The percentage greater than the 1000 MWM is y,G = 3.98 - 0.48 x (100) = 88 3.98 Using this method of calculation, the percentages in the'different molecular weight fractions are as follows: < 1000 MW = 12 (100-88);
>1000 <10,000 MW = 40 (88-48); <10,000 >100,000 MW = 23 (48-25);
>100,000 MW = 25.
- f.3. GOTG15tD7 PRINTI54 CFFICII 1980-0-%1-7W./566 LLL 1980/11 66 e
NRC rcau 335 1.
R N MS R Harriedeer DOC /
U.S NUCLEA*2 REGULATORY COMhel8880N n.nl NUREG/CR-0750 BIBLIOGRAPHIC DATA SHEET UCRL-52706
- 1. TITLE AND SUBTITLE Maw vabme Na,iteprapnes; g g,,,,,j Concentration and Speciation of Copper in Waters Collected Near the San Onofre and Diablo Canyon Nuclear Power Stations 3. REclPIENT3 ACCESSION NO.
- 7. AUTHORIS)
- 6. DATE REPORT COMPLE.TED F. L. Harrison, D. J. Bishop, R. R. Emerson, & D. W. Rice, J
. e rn august L,1980 aAm
- 9. PERFORMING ORGANIZATION NAME AND MAILING ADDRESS # ache Ew Coel DATE REPORT ISSUED Lawrence Livermore National Laboratory
- lvana wo~rn 7000 East Avenue November 1980 Livermore, Ca 94550
- s. nea, m ias
- s. nome mens
- 12. SPONSORING ORGANIZATION NAME AND, MAILING ADORESS # ache le Coel U.S. Nuclear Regulatory Commission Office of Nuclear Regulatory Research 7
SAFER Division Washington, D. C. 20555 FIN No. A0119
- 13. TYPE OF REPORT PE maDD CovEmED #ackene elemsf Topical
- 15. SUPPLEMENTARY NOTES
- 14. Rome m en) 1s. AssTRAcT aoo..re er seul Concentrations and physicochemical forms of copper were determin ed in seawater collected in the intake and discharge areas of the San Onofre and Diablo Canyon Nuclear Power Stations..At the San Onofre Stat' ion, which has half copper-nickel and half titanium tubing in its c.ooling system, 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, which has only titanium tubing in its cooling system (except for that in an auxiliary system), copper concentrations ranged from 0.6 to 2.3 ug/L. The San Onofre Station has a long operational his, tory, whereas the Diablo Canyon Station has never generated electricity. Copper concentrations in effluent waters at San Oncfre wer3 usually higher than those in waters from control and intake areas, but differences were small. During start-up of water circulation through the condensers at Diablo Canyon after start-up of the main circulators, the copper concentration in the effluent water was about 28 pg/L, but decreased rapidly & reached normal levels after about 3 h.
Cepper in the particulate fraction of the discharge waters ranged from less'than 10 to 75% of the total. Copper in the soluble fraction was primarily in bound forms. The apparent complexing capacity was approximately 1 pg Cu/L; soluble organics gnged from 1.2 to 2.5 mg C/L. Ultrafiltration of discharge waters radiolabeled with Cu indicated that, in most samples, less than 20% of the copper was in chemical forms reported to be available It'xhPd8RDNd%OcW(NT A
SI'S-7e DE RI TO Copper San Onofre, Toxic Substances Aquatic Environment Diablo Canyon Nuclear Station Discharges Nuclear Power Station Discharges of-Copper Chemical Forms 17th IDENTIFIERS /OPEN4NDED TERMS
- 18. AVAILABILITY STATECENT
- 19. MCURITY CLASS As sportl
- 21. NO. OF P AGES Hnciassified Unlimited ansECURITY,CW A4papel
- 22. Prim Unclassified s
cac ronM ass p-ni JL