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Marine Chemistry, 38 (1992) 165-184

Elsevier Science Publishers B.V., Amsterdam

165

The behaviour of a Cu (II) ion selective electrode in seawater; copper consumption capacity and copper determinations
D.A. Rom~inand L. Rivera
Departamento de Qulmica, Facultad de Ciencias Bdsicas, Universidadde Antofagasta, Campus Coloso, Casilla 170, Antofagasta, Chile
(Received 3 May 1990; revision accepted 31 January 1992)

ABSTRACT Rom~in, D.A. and Rivera, L., 1992. The behaviour of a Cu(II) ion selective electrode in seawater; copper consumption capacity and copper determinations. Mar. Chem., 38:165-184. Determinations of copper consumption capacity (CuCs.C) and labile copper concentrations in surface coastal seawater, using a copper ion selective electrode (Cu-ISE) potentiometric method under predominantly diffusive conditions, are reported. For evaluation of the copper concentrations, the points of the endpoint contiguity zone of the CuCs.C titration curve were treated by an ISE multiple standard addition technique. The results were compared with those obtained by means of a Chelex- 100 (calcic form) 'batch' procedure-potentiometric stripping analysis. The labile copper of the sample was determined at concentrations down to 10.70 nM with an average RSD of 12%, independent of the Cu-ISE employed. For adjacent subsamples, the mean CuCs.C values obtained for El Way seawater were equivalent to 81.05 and 48.00 nM copper, with an RSD of 4 and 7%, and for Isla Santa Mafia seawater the value was equivalent to 70.27 nM copper, with an RSD ef 7%. The theoretical approach of the electrode diffusive mechanism proposed, which would depend, fundamentally, on the adsorptive, complexing and reducing properties of the dissolved organic matter in the seawater sample, allows simultaneous analytical determination of CuCs.C and labile copper concentration in seawater.

INTRODUCTION

In copper(II) potentiometric measurements using a copper ion selective electrode (Cu-ISE) with a membrane composed of pure copper sulphides and copper(II) sulphide mixed with silver sulphide, generally the electrode behaviour is non-Nernstian in real analytical samples (Lewenstam et al., 1985 ). This has been observed in attempts to determine the copper concentration in seawater samples (Jasinsky et al., 1974; Oglesby et al., 1977). Thus, in spite
Correspondence to: D.A. Rom~in, Departamento de Quimica, Facultad de Ciencias B~isicas, Universidad de Antofagasta, Campus Coloso, Casilla 170, Antofagasta, Chile.

0304-4203/92/$05.00 1992 Elsevier Science PublishersB.V. All rights reserved.

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D.A. ROM,6aNAND L. RIVERA

of agreement among the potentials measured, the analytical results obtained are not very reliable, and according to Zirino and Seligman ( 1981 ) should be considered as approximate. The non-Nernstian response of the Cu-ISE in seawater is due, fundamentally, to the presence of chlorides (Oglesby et al., 1977; Westall et al., 1979; Zirino and Seligman, 1981 ), and is manifested as the dependence of the measured potential on the rate of stirring of the sample solution (Jasinsky et al., 1974; Zirino and Seligman, 1981 ). This problem has diminished the interest in these devices as analytical tools, particularly in chloride- and bromide-enriched samples, but at the same time has stimulated studies on the Cu-ISE response mechanism in the presence of interference (Lewenstam et al., 1987 ), and in the practical analytical utilization of the super-Nernstian electrode slope involved in a semi-empirical or modified Nernst equation (Lewenstam et al., 1985). The halide interference is manifested through parasitic reactions that occur on the electrode sensor surface. In electrodes with pure Cu2S membranes the most important reaction should be (Hepel, 1982; Lewenstam et al., 1985 ) Cu2S + Cu 2+ + 2 n X - ~ C u S + 2CuX~ -n ( 1)

if the influence of redox processes is not considered. In another approach, the predominant reactions should be redox processes with participation of the material of the membrane electrode (e.g. Westall et al., 1979; Lewenstam et al., 1985): CuS + Cu 2+ + 2 n X - ~ 2CuCI~- n + S (2)

The presence of electroactive AgC1 has also been confirmed in the electrode membrane surface (Lewenstam et al., 1985). According to Westall et al. (1979), the non-Nernstian Ag2S/CuSmembrane electrode response in chloride-containing media is due to a one-electron transfer between Cu at the electrode surface (present as an impurity) and Cu 2+ in solution, forming cuprous ion. However, these theoretical considerations account for a range of concentrations that are far greater than the range of copper concentrations found in seawater, and account for neither the non-Nernstian Cu ( II )-ISE behaviour in the transition zone between the formal response domains of the electrodes (namely, 29 and 59 mV per decade) nor the super-Nernstian responses (over the 59 mV per decade response domain). Measurement of the so-called copper complexing capacity (CuCC) is highly controversial, but the potential importance of this complexing parameter is acknowledged in the field of dissolved metal speciation (Hirose and Sugimura, 1985; Buckley and Van den Berg, 1986; Hering et al., 1987). Copper (II) is generally chosen for determination of seawater complexing or the metal binding capacity, Lx, because Cu(II) forms relatively stable copper compounds with the ligands present and because it may be determined by

Cu(II)-ION SELECTIVEELECTRODE BEHAVIOUR

167

numerous analytical methods. However, these methods all have theoretical and practical limitations (Kramer, 1986; Moffett and Zika, 1987; Hering et al., 1987). The seawater CuCC is defined as the ability of the sample to remove the added copper from the pool of metal ions, representing, fundamentally, the total organic ligand concentration, LT. Therefore, this concept must be clearly differentiated from the 'copper consumption capacity' (CuCs.C), that is to say, the amount of metal consumed directly by the sample, expressed in moles per litre. Cu(II)-ISE potentiometric techniques are suitable for determining the CuCC and copper-binding properties of sample solutions poor in chlorides, such as fresh waters and reconstituted solutions containing isolated natural organic ligands from soil and algal exudates (Buffle et al., 1977; Bresnahan et al., 1978; McKnight and Morel, 1979; Stella and Ganzeril-Valentini, 1979; Sunda and Hanson, 1979; McKnight and Morel, 1980; Saar and Weber, 1980; Buffle et al., 1980; Gamble et al., 1980; Cabaniss and Shuman, 1986; Fish and Morel, 1985; Sweileh et al., 1987). However, it has been reported that these methods are not suitable in seawater because of a strong Cu-ISE interference from the high chloride ion concentration (Buffle et al., 1980; Waite and Morel, 1983; Lund, 1986; Cabaniss and Shuman, 1986; Fitch et al., 1986; Sweileh et al., 1987), and their related problems as mentioned above. Nevertheless, Westall et al. (1979) have shown that in unstirred seawater samples spiked with NTA, which have been allowed to approach equilibrium in the region next to the electrode surface, it is feasible to measure the total copper concentration and the CuCC. Ideally, trace metal speciation measurements should be conducted in situ, thereby preventing any alteration of the dynamic natural state of the metal species, and any realistic discussion must also be concerned with the role of particulate matter (Andreae, 1986). The ideal analytical method would determine species directly in situ, non-invasively and non-destructively, but to date all methods employed are invasive, to varying extents, and frequently their validity is only operational. The theory behind these methods is poorly understood (Bernhard et al., 1986 ). The studies of Cu-ISE response in seawater have been limited, fundamentally, to the interference effect of the chloride ion. On the basis of previous data (Westall et al., 1979; Lewenstam et al., 1985 ), the following interference mechanisms have been proposed for various types of Cu-ISE: Ag2 S + Cu 2+ + 4nX- ~ 2AgX ~- n + 2CuX~- n + S CuS+Cu 2+ + 2nX- ~2CuX~ -~ +S
C u 2 S + 2Cu 2+ + 4nX- ~4CuX~ -~ +S

(3) (4) (5)

These reactions explain the interference processes on the membrane surface, and the poor reproducibility and instability of the potential response, as the

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D.A. ROMAN AND L. RIVERA

result of the formation of elemental sulphur. The amorphous sulphur formed could mechanically block the electrode surface and may cause the irreversibility of reactions ( 3 ), (4) and (5). It becomes obvious that direct determination of copper in ttie presence of high concentrations of chloride or bromide ions is impossible in stirred solutions. However, the Cu-ISE response without stirring and under the influence of some reducing agent (Smith and Manaham, 1973; Westall et al., 1979; Lewenstam et al., 1985 ) may overcome certain interference effects, and improve the reproducibility and the stabilization of the potential measured. In unstirred chloride-containing solutions, diffusion to and from the electrodes predominates. Therefore, the electrode mechanisms which control the Cu-ISE response in natural seawater, where mass transport occurs fundamentally by means of diffusion, are not yet fully understood. Smith and Manahan (1973) have reported that the attainment of stable potentials in tap-water and freshwater samples required the presence of a mild reducing agent, and they used formaldehyde. Further, Zirino and Seligman ( 1981 ) showed a 'polarographic' behaviour of Cu (II)-ISE in seawater. The copper(I) electrode function of Cu-ISE has also been demonstrated (Neshkova and Sheytanov, 1985 ). Otherwise, the effects of discrete organic ligands such as EDTA (ethylenediaminetetraacetic acid) on Cu-ISE response in nonmarine samples, in which the ligand is in excess, have shown abnormal behaviour of the electrode (Fitch et al., 1986 ). The state of knowledge of the Cu-ISE behaviour in seawater is limited; the applications under conditions with stirring are hardly reliable and'do not represent the behaviour of copper in seawater. For instance, the results obtained by Rosen and Williams (1978), which demonstrated that marine fulvic acid isolated from coastal seawater does not complex Cu 2+ ions in seawater, are in contradiction to the actual state of knowledge. We know that copper organic species exist in marine waters and that they correspond to a significant fraction of the total dissolved copper concentration of seawater (Sunda and Hanson, 1987). Selective molecular components of the seawater dissolved organic matter (DOM) responsible for copper complexation have been only partially identified and characterized. Some lower molecular weight (molecular weight less than 220) trace compounds, such as free amino acids and carbohydrates, also have the required organic functions to complex metal (Simoes Goncalves and Valenta, 1982; Simoes Goncalves et al., 1983; Haas, 1986), but the degree to which they complex metal ions in seawater is not known. Dissolved macromolecular humic substances constitute a significant fraction of the uncharacterized DOM. These substances are relatively hydrophobic and are generally considered the most important copper complexing compounds of coastal seawater (Raspor et al., 1984). To date, however, the influence of humic substances on the ISE response has not been adequately examined (Fitch et al., 1986). Lewenstam et al. (1985) have shown that in the presence of an adequate

Cu(II)-ION SELECTIVEELECTRODE BEHAVIOUR

169

complexing and reducing reagent, which binds Cu (II), Cu (I) and Ag (I) more strongly than chloride and bromide, the exchange reactions at the membrane Cu-ISE-solution interphase are stabilized, permitting the analytical utilization of the super-Nernstian slope electrode in determining the copper concentration of the sample. However, faced with an eventual application in seawater, it is important to determine whether the total concentration or that of a particular copper species is being determined. We propose a Cu-ISE potentiometric research method, by means of which, in unstirred membrane-filtered surface coastal seawater and at the natural pH of the samples, it is feasible to determine the CuCs.C and the labile dissolved copper concentration of the samples. For this last goal, the copper additions at the CuCs.C titration endpoint contiguity zone were treated by an ISE multiple standard addition technique. The copper concentrations thus obtained were compared with the results obtained by a Chelex-100 (calcic form ) 'batch' procedure-potentiometric stripping analysis (PSA). A description of the super-Nernstian electrode behaviour, considering the influence of seawater complexing organic substances on Cu-ISE response, and the practical utilization of the super-Nernstian slope electrode are also proposed and discussed. THEORY The Cu-ISE behaviour in seawater under unstirred conditions would be fundamentally determined by surface-active properties of the seawater DOM. The membrane electrode would behave in a similar way to certain seawater suspended solids (Hunter, 1980; Plavsic et al., 1987; Zutic and Tomaic, 1989 ) and its adsorptive interactions with DOM at the membrane electrode-seawater interphase would occur in such a way that membrane solubilization should be disfavoured. For some time it has been acknowledgedthat the characteristic surface charges exhibited by solids in seawater are due to adsorbed organic constituents (Neihof and Loeb, 1974). In particular, dissolved polymeric substances have the required properties for this interaction (Hunter, 1980). Proteinaceous and humic substances derived from the degradation of natural products of marine origin are surface-active polymers carrying a net negative charge at the pH of seawater (Neihof and Loeb, 1974). The organic coating of electrodes made from other materials, such as platinum surfaces, immersed in natural seawater has also been shown (Kristoffersen et al., 1982 ). Recently, Hars~inyi et al. (1987) have shown a composition change of the Cu (II)-ISE membrane in solutions containing chloride ions; this finding indicates chloride uptake into the membrane phase at low copper ion concentration if the solution is not stirred. Also, a few studies have considered the redox properties of fulvic and humic materials (Skogerboe and Wilson, 1981; Moffett and Zika, 1983; Millero, 1985; Moffett et al., 1985). In the electrode mechanism proposed below, the rate production of Cu (I)

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D.A. ROM,~N AND L. RIVERA

could be increased by organic ligand-metal charge transfer processes at the electrode membrane surface, which could be catalysed by chloride ion. Cu (II) and Cu (I) would be stabilized by complexation. Also, effects of the ionic salts on the stability of pol~cmeric seawater DOM could be important in this approach, similar to their effects on the conformational stability of macromolecules such as proteins (Damodaran and Kinsella, 1981 ). The basis of all the so-called stripping techniques is the preconcentrationmeasurement sequence with a working electrode; thus a number of papers have described variations of this approach, in which analyte preconcentration is carried out at chemically modified electrodes whose surfaces have the ability to react with and bind the analyte (Prabhu et al., 1987). Consequently, no potential needs to be applied. Something similar could occur with the Cu-ISE immersed in natural seawater, as a result of the interaction between the electrode membrane and the DOM of the media. In the bulk of the seawater, DOM must be present free and as metal complexes, including of course the copper complexes, whereas in the copper selective membrane surface under unstirred measurement conditions, copper (I) would be formed and should be complexed immediately by the adsorbed organic ligand on the electrode membrane. Chloride ions should catalyse the electron transfer towards C u ( I I ) from ligand L adsorbed on the polarized electrode membrane, resulting in super-Nernstian electrode responses. Such chloride effects have been shown in voltammetric measurements of Cu (II) organic interaction in estuarine waters (Nelson (1985a,b) and references cited herein), in which CuCI~- is involved also. The following simplified model reactions could account for the mechanism proposed: CuS (s) + L(aq) -+ CuS-L (s) C u S - L ( s ) + C u 2+ ( a q ) ~ C u S - L - C u 2+ (s) C u S - L - C u 2+ (s) + 2 CI- (aq) --, CuS-L-CuC12 ( s ) (6) (7) (8)

Similar model reactions would account for the copper selenide electrode membrane behaviour. The presence of a non-adsorptive and non-reducing strong cupric complexing ligand might affect this mechanism only if the ligand is able to out-compete chloride ion for control of copper at the electrode surface. Formally, the copper ion selective electrode has two modes of response: 29 mV per decade in the absence of chloride, and 59 mV per decade in media of high chloride concentration (Westall et al., 1979). If the electrode is in this last mode, it is impossible to measure cupric ion activity; only copper in the form of cuprous ions can be measured. Consequently, the non-Nernstian responses would comprise the electrode response in the transition zone between the two above-mentioned domains and those that overcome the 59 mV per decade domain, which are also called super-Nernstian..

Cu (II)-ION SELECTIVE ELECTRODE BEHAVIOUR

171

In the results given below, the Cu-ISE responses in coastal seawater are super-Nernstian. The above remarks pertain to unstirred seawater, which has been allowed to approach equilibrium in the region next to the electrode surface. The Cu-ISE super-Nernstian response would depend fundamentally on the 'primary quality' of the seawater DOM, which generally is in excess in surface coastal seawater with respect to the copper concentration of the media. In this work we assumed that the copper reduction at the electrode surface affects the labile dissolved copper concentration only; thus the CuCl~- -L complex concentration equals the labile fraction of the metal in the sample. Otherwise, the endpoint of the seawater copper titration is interpreted as the 'copper consumption capacity' of the sample, because other reactions, such as displacement metal reactions, could be involved also. For example, calcium might already be bound to the ligand and be replaced by copper. The adsorptive, complexing and chloride-catalysed reducing properties of DOM in seawater would minimize or eventually eliminate the Cu-ISE membrane corrosion caused by halides. Typical CuCs.C titration curves are presented in Fig. 1. The copper additions considered at the endpoint titration contiguity zone, for the evaluation of the labile copper concentration by the standard addition technique, are indicated. Before the titration equivalent point, copper speciation would be controlled in the bulk solution by DOM and in the interphase by eqns. ( 6 )- ( 9 ). After the titration equivalence point, although the concentration of cupric ion is high enough, the electrode process could be represented also by the reaction CuS-L-CuCI~- (s) + Cu E+ + 2C1- ~ CuS-L-CuCI~- (s) + CuC12
E (mY) Z 10 Cu I I S E vs S C E 150 130 110 90 70 50 0
I I ,I I I I

(9)

8 6 4 2 0 40

10

16

20

28

30

36

V x E-3 (ml)
*A
Orlon 9 4 - 2 9 (A, El Way; B, Isla 8to. Maria) and Radiometer F-1112 (C, El Way) Cu-18E were uoed.

+ C

Fig. 1. Seawater CuCs.C titration and multiple standard addition determination of copper.

172

D.A.ROMANAND L. RIVERA

Based on the diffusion model and its assumptions (Lewenstam et al., 1985 ), and considering the electrode mechanism outlined in this work, the following working Nernst equation for the potentials of the Cu-ISE in seawater under unstirred conditions is proposed: E='constant'+SsN log A [CuCs.C](~/k)2

Co.

(10)

This equation was employed in the linearization of the endpoint contiguity zone of the CuCs.C titration curve. Cc, is the unknown copper concentration; SsN the experimental super-Nernstian electrode slope obtained from E vs. pCu plots (pCu= - l o g [ C u 2+ ]aaded; see Fig. 2 ); A is an operational parameter defined as the inverse of the SsN/SN ratio (k), in that SN is the 29.5 mV per decade Nernstian mode electrode response; the 'constant' term represents the conditional potential of the electrode system in the experimental conditions described, related to the potential of the seawater sample E. Pursuing arguments similar to those of Smith and Manahan ( 1973 ), but considering the above super-Nernstian focus, the following multiple standard addition linear function was assumed:
10En-EO/SSN- 1 = Z - 1 - A [ C u C s . C ] ( 1 / k ) 2 x C S X VS Vo X Cc.
(

11 )

This equation indicates that, in this case, the seawater labile copper concentration, Ccu, may be preferably determined from the slope of a plot of Z - 1
160 140 120 lO0 80 6O 4o 2o
I !

E vs 8CE (mY)

6.6

7.6

piC.] (u)
-'*- A Orion 04-2g (A El WRy; B, Ioia 8la. Maria) ~ RadkHItelor F-11'1~(C, El Way) Cu-18E m u n d . n B * C

Fig. 2. Seawater CuCs.C titration endpoint contiguity Cu-ISE potentials. Diffusive conditions.

Cu (If)-ION SELECTIVE ELECTRODE BEHAVIOUR

17 3

vs. Vs where several standard additions are made. En are the Cu-ISE measured potentials in the 110subsample when the copper standard addition volumes (Vs) of one copper standard solution (Cs) have been made. k would represent the Cu (II)-ISE experimental Nernstian deviation, and we suggest that k could be in some way associated with the primary chemical properties of the seawater DOM responsible for the electrode process also. A would be related to the diffusion coefficients of Cu (I) and Cu (II) complexes, D' and D" respectively, which cannot be determined exactly because of lack of values for the diffusion coefficients of copper free ions in seawater media. If the Cu ( II ) - D O M membrane surface formed complex and the Cu ( II ) - D O M bulk solution complex coexist at the Cu-ISE membrane-seawater interphase, then the fluxes of both complexes should be equal. Therefore, we can write the following equation if 1 : 1 stoichiometric ratios are considered: D" ( [ C u ( I I ) L ] - [ C u ( I I ) L ] s ) = D ' ( [ C u ( I ) L ] - [ C u ( I ) L ] s ) (12)

If an approach such as that of Lewenstam et al. (1985) is considered, A is approximated by the expression

A=qO'/O'

(13)

in which q is a fitness parameter that should reflect the deviation of D"/D' caused by the DOM complexation of Cu (I) and Cu (II), respectively. This being the case, in the absence of complexing ligand, the D"/D' ratio is 0.45 (Lewenstam et al., 1985 ); then q may be evaluated if A has previously been found.
EXPERIMENTAL METHODS

Apparatus
Potential measurements were made with a Radiometer (Copenhagen) pH meter 26 (expanded scale) with a Radiometer K-701 double junction reference electrode. Equilibration potential readings were taken in unstirred solutions when the rate of potential drift was less than 1 mV h - 1. Two copper ion selective electrodes were used: the Radiometer Selectrode (Copenhagen) model F-1112 (Cu~.aSe) and the Orion (Cambridge, MA, USA) model 9429 A (CuS/Ag2S) cupric ion selective electrode. The working electrodes were polished before each CuCs.C titration run, according to the instructions supplied by Radiometer and Orion. All measurements were made at 25 _+0.5 C in Radiometer V-533 and V-535 glass cells thermostatted by means of water circulating (Haake (Berlin, FRG) circulator model FK) through the cell jacket, accommodated on a Radiometer TTA-80 titration assembly. The cupric ISE responds to light and 02 (Westall et al., 1979; Buffle et al., 1980; Zirino and Seligman, 1981 ), so measurements were run under constant illu-

174

D.A. ROMAN AND L. RIVERA

mination (a small a m o u n t of methylene blue chloride was added to the circulating water) and O2-free conditions. N2 free from oxygen, purged through a 1 M NaOH saturated pyrogallol solution, was passed over the solution at low rates to minimize gas flow induced circulation of the sample solution during all the measurements until the equilibration potential was reached. At the start of each series of measurements the ISE was polished and then treated as follows: it was kept for 1 h in a stirred 1 X 10-3 M EDTA solution, prepared in KNO3 solution with a conductivity at 25 C equivalent to seawater (ionic strength buffer), for 0.5 h in a stirred EDTA-copper solution ( 4 X l 0 -6 M Cu 2+ and 6X l 0 -6 M EDTA), then for 0.5 h without stirring in this same solution, and finally with deionized water. This treatment was adequate for the Orion Cu-ISE in all measurements of each of the CuCs.C titrations. However, for the Radiometer Cu-ISE it was better to employ a copperEDTA solution (6 10- 6 M Cu 2+ and 4 10- 6 M EDTA), for the copper (II) additions after the endpoint zone of the CuCs.C titration. After each measurement of the series of copper (II) additions (five to seven per CuCs.C titration ), the Cu-ISE membranes were cleaned with pieces of felt which had previously been washed. When not in use the Cu-ISE electrodes were stored dry. The outer electrode compartment of the calomel double-junction electrode was filled with KNO3 ionic strength buffer; seawater was used instead of the KNO3 solution in some CuCs.C titration experiments. Saturated KCI and KNO3 solutions were prepared from KC1 and KNO3 solutions that had previously been passed through a bed of Chelex- 100 resin (Bio-Rad, Richmond, CA, USA), potassium form, to remove trace metals. When not in use the calomel double-junction electrode was stored in KNO3 ionic strength buffer solution. For potentiometric stripping analysis a Radiometer ISS-820 analyser was used. Radiometer TTA-80 titration units equipped with Radiometer V-534 and V-540 glass cells were employed as electrochemical cells. The working electrode was a Radiometer F-3500 glassy carbon electrode. A double-junction Ag/AgC1 electrode (Orion 90-02 with filtered seawater in the outer chamber) was used as a reference electrode, and a platinum foil (Radiometer P- 1312 ) was used as counter electrode. The copper additions were made with a digital Brand (Wertheiry-Glashtitte, Germany) Transferpettor micropipette. The seawater and KNO3 ionic strength buffer solution were checked in a Radiometer CDM 2e conductimeter with one CDC 104 standard cell at 25 C. All labware and polyethylene bottles used for handling the seawater samples were cleaned with Extran MA 01 (Merck) detergent solution, rinsed with distilled water, soaked overnight in 6 M HC1, rinsed with distilled water, soaked overnight in 0.01 M EDTA, rinsed with distilled water and organic matter free deionized water.

Cu(II)-ION SELECTIVEELECTRODE BEHAVIOUR

175

Reagent and chemicals

In Cu-ISE measurements, all Cu (II) additions were made from diluted 0.01 M Cu(NO3)E.X3H20 (Merck, Darmstadt, FRG) (p.a.) stock solution standardized against EDTA. Chemicals used in PSA copper determinations, except Hg ( II ) nitrate (p.a.), were of Suprapur grade (Merck), and all Cu (II) additions were made from conveniently diluted Cu (II) Merck Titrisol ampoules. All other chemicals were reagent grade. Distilled water passed through a Coming (New York, USA) 3508 high-purity demineralizer cartridge was used in all the work.
Seawater samples

Surface coastal seawater samples were collected by hand with 2 1 polyethylene bottles at two locations, E1 Way and Isla Santa Maria, off the coast of Antofagasta. The samples were immediately filtered (0.45/~m ) through acidwashed Sartorious (Gottingen, Germany) SM-111 membrane filters of 47 mm diameter (Nucleopore (Pleasenton, CA, USA) polycarbonate filterholder). For each 1 1 subsample a new filter was used. The first 100 ml of filtrate was used to rinse the receiving flask and was then discarded. The subsamples were immediately subjected to the analytical procedures.
Procedures CuCs. C D titrations Thirty millilitres of filtered seawater were dispensed into a thermostatted cell placed in the TTA-80 titration unit, which was stirred until a constant potential variation was reached (this took approximately 1 h), and one copper(II) diluted standard solution addition was made (4.0-12.0/A of (1.52.0) 10 -4 M copper standard solution) with continuous stirring for approximately 1 h until a constant potential variation was reached. The stirring was then stopped, leaving the sample undisturbed until the operational equilibration time was reached. Each measurement of every CuCs.C titration was made in a similar manner, adding copper solution to separate 30 ml aliquots of filtered seawater subsamples (two times, three times the first copper addition volume, and so on). As the equilibration potential times were long, and to minimize the effects of copper adsorption on the container wall, the measurements were not made on the same 30 ml seawater aliquot. Furthermore, only duplicates of CuCs.C titration per sample were considered. The sample was maintained at 4-5 C during the time of analysis. The CuCs.C titration endpoint volumes were found by the second derivative method. Copper concentration by ISE Using eqn. ( 11 ), the labile dissolved copper concentration in the seawater

176

D.A. R O M A N A N D L. RIVERA

was evaluated by a multiple standard addition potentiometric technique (Smith and Manahan, 1973). The CuCs.C titration endpoint volume contiguity zone potential measurements and the respective super-Nernstian slope were considered. The potential of the copper electrode compared with that of the reference electrode of the sample solution, E0, was evaluated by extrapo-

FIL~ SIgA~I~I~

~c u" detemined~

C~L~-IM(Ca)~

CaCs.C and C
CU

Delia, mined

l~ the ~(II)-ISEmtl~l prOlmedin this ~ k . (b)

C
CU

m taken for the

resin,

Determined

Fig. 3. Experimental approach. (a) represents the total dissolved copper concentration. (b) represents the labile dissolvedcopper concentration.

Cu (II)-ION SELECTIVEELECTRODEBEHAVIOUR

17 7

lation from a least-squares adjusted plot of E vs. copper addition volumes of a diluted copper standard solution for the appropriate seawater CuCs.C titration endpoint volume contiguity zone.

Copper concentration by PSA


Aliquots (40 ml ) of filtered acidified seawater (0.015 M HNO3, Suprapur grade) were employed to determine the total dissolved copper concentration and the copper concentration of the metal not taken up by the resin in the samples, following the experimental conditions of Jagner and Aren(1979) and Jagner et al. ( 1981 ). The plating times chosen were 3 h 4 min and the measurements were made in separate aliquots, to minimize the effects of metal adsorption on the container walls. The copper concentrations were evaluated by means of the normal standard additions equations (Bader, 1980).

Chelex- 1O0 (calcicform) batch procedure


These experiments were performed in a manner similar to that of Figura and McDuffie (1979), except that in this case 1 1 seawater subsamples and 5.2 g of resin were employed. Ca-Chelex was prepared according to the procedure of MacKey ( 1983 ), employing HNO3, HC1 and CaCIz, Suprapur grade (Merck). The Ca-Chelex resin was rinsed with deionized water until Ca (II) assay with calcein in the wash solution produced negative results. In Fig. 3 the experimental approach of this work is shown.
RESULTS A N D D I S C U S S I O N

The CuCs.C and Ccu results for the surface coastal seawater under study are shown in Tables 1 and 2, assuming a 1 : 1 copper ligand stoichiometric ratio. These results represent the total copper consumption for the seawater subsamples, and the dissolved labile copper concentrations in the media, respectively. The F test shows that there are no significant differences between the results obtained by the Orion 94-29 A (CuS/Ag2S) and the Radiometer F-I 112 (CUl.aSe) Cu-ISE. Figure 2 shows linear plots for the copper additions at the endpoint titration contiguity zone corresponding to the cases shown in Fig. 1. Table 3 shows the experimental SsN slope values and the calculated parameters for and from eqn. (10), including the evaluation of q from eqn. (13) determined using the data reported in Table 2. It appears that the values of the q parameter obtained show that the DOM copper complexation in E1 Way and Isla Santa Maria seawater is determined by the organic ligands inherent to each medium, and is independent of the Cu-ISE employed (see Table 3 ). The copper concentrations found in surface coastal seawater subsamples determined by means of the Cu-ISE method developed in this paper would correspond to the labile copper fraction of total dissolved metal. In Table 4

178 TABLE 1

D.A. ROMANAND L. RIVERA

Copper (II) consumption capacity determination results for surface coastal seawater from El Way and Isla Santa Maria Set samples 1(09/24) a 2 (10/01) 3 (10/03) 4 (11/07) b 5 (11/12) 6 (11/14) 7 (11/25) c 8(01/11) 9 (01/13) 10 (01/15) CuCs.C (nM) 165.3 78.7 83.4 70.8 50.4 45.6 88.1 66.1 69.2 75.5 SD RSD (%)

3.3

4.1

3.4

7.1

4.8

6.8

aA Radiometer F-1112 Cu-ISE was employed in measurements on subsamples 1-3 (El Way). bAn Orion 94-29 Cu-ISE was employed in measurements on subsamples 4-6 (El Way). CAn Orion 94-29 Cu-ISE was employed in measurements on subsamples 7-10 (Isla Santa Maria). Numbers in parentheses indicate the date on which the sample was removed; samples were analysed immediately. TABLE2 Primary data and copper determination results for surface coastal seawater, obtained by means of CuISE standard addition potentiometric method Set samples 1 2 3 4 5 6 7 8 9 10 (09/24) a (10/01) (10/03) (11/07) b (11/12) (11/14) ( 11/25) (01/11) (01/13) (01/15) E (mV) subsample 85.6 99.5 92.0 118.3 97.4 97.5 175.0 134.0 116.5 128.1 Super-Nernstian slope (SsN) 66.1 82.0 80.6 67.1 72.5 73.0 132.6 147.7 114.6 132.5 k Ccu

(SsN/SN)
2.2 2.8 2.7 2.3 2.5 2.5 4.5 5.0 3.9 4.5

(nM)
10.70 8.03 8.18 7.55 10.07 9.92 3.93 5.98 8.50 7.40

"A Radiometer F-1112 Cu-ISE was employed in measurements on samples 1-3 (El Way). ban Orion 94-29 Cu-ISE was employed in measurements on samples 4-6 (El Way). CAn Orion 94-29 Cu-ISE was employed in measurements on samples 7-10 (Isla Santa Maria). Numbers in parentheses indicate the date on which the sample was removed; samples were analysed immediately.

are presented the results of subjecting the subsamples to the Cu-ISE method and a Chelex-100 (calcic form ) batch procedure. The major compositions of the subsamples are given in Table 5 (Ramirez, 1986; Mifio and Torres, 1986).

Cu (II)-ION SELECTIVEELECTRODEBEHAVIOUR TABLE3 Experimental and calculated parameters for and from eqn. (10) Samples a, b 1 2 3 4 5 6 7 8 9 10 Constant (mV) -83.2 - 104.9 -95.9 -112.9 - 106.3 -95.5 - 176.9 - 171.5 -148.7 - 166.7 SsN A

179

66.1 82.0 80.6 67.1 72.5 73.0 132.6 147.7 114.6 132.5

1/2.2 1/2.8 1/2.7 1/2.3 1/2.5 1/2.5 1/4.5 1/5.0 1/3.9 1/4.5

1.01 0.79 0.82 0.97 0.89 0.89 0.49 0.44 0.57 0.49

Radiometer F-1112 Cu-ISE was employed in measurements on samples 1-3 (El Way). An Orion 9429 Cu-ISE was employed in measurements on samples 4-10 (4-6, El Way; 7-10, Isla Santa Maria). TABLE4 Copper concentration results for surface coastal seawater, determined by means of Cu-ISE potentiometry and potentiometric stripping analysis

Set samples
Ccu Cu-ISE (nM) + SD RSD (%) PSA (nM) _+SD RSD (%) PSA (nM) + SD RSD (%)

E1 Way a

E1 Way b

Isla Santa Maria b 6.45 0.99 15 29.43 6.77 23.0 35.25 4.88 13.8

Ccu

batch effluent
Ccu (c)

8.97 1.04 12 33.99 4.72 13.9 42.97 4.41 10.3

9.12 0.82 9 -

aA Radiometer F-I 112 Cu-ISE was employed. (See Table 2. ) bAn Orion 94-29 Cu-ISE was employed. (See Table 2. ) CTotal dissolved copper concentration. (For further explanation, see the text. )

Consequently, approximately 20% of the total dissolved copper concentration of the subsamples is part of the so-called labile metal fraction, although it is possible that some copper species of medium lability are included also. The effluents of the Chelex-100 batch procedure were tested using the Cu-ISE technique, with negative results, which fQrther confirms the findings previously mentioned. According to our results, some bodies of surface coastal seawater of the Antofagasta region show a transient enrichment in copper, presumably as a result of untreated metallogenic wastes from various copper industry plants.

180 TABLE 5 Major composition of E1 Way and Isla Santa Maria seawater El Way Chlorinity (%o) Salinity (%0) Alkalinity ( M 10 -3) pH C1- (gl - j ) SO ] - (gl - l ) Na + (gl -~ ) K + (gl - l ) Ca 2+ (g1-1 ) Mg 2+ (gl - j ) 19.5 35.2 2.27 7.98 18.73 2.74 10.25 0.43 0.44 1.39 Isla Santa Maria 19.5 34.5 2.34 8.07 18.56 2.65 8.76 0.33 0.37 1.33

D.A. ROM~.N AND L. RIVERA

As will be shown in a later paper, in seawater subsamples taken at the dump sites, the Chelex-100 batch procedure-PSA shows that less than 20% of the total dissolved copper concentration is found in a non-labile metal form. Regardless of the method employed to determine 'copper complexing capacity', the results obtained by each method must represent the total ligand (s) concentration, LT, available for the formation of stable metal species in the seawater. According to Hirose and Sugimura (1985), the seawater organic ligand concentration obtained by titration of ligand by one metal (the MT method) should be higher than the results secured by means of a method in which the metals are titrated by ligands (the LT method). LT is, in general, a difficult parameter to measure by any method, and the examination of the error propagation equation leads to the observation that the least error results from methods that most directly measure the CuCC (Fish and Morel, 1985 ). We consider that the direct methods, as developed in this work for measuring the 'copper complexing capacity' of seawater, determine the 'copper consumption capacity' of the soluble fraction of seawater. Many workers have discouraged the use of the term 'complexation capacity' (often used synonymously with 'binding capacity') because of potential ambiguities (Lund, 1986). The CuCs.C, like the CuCC (Nfirnberg, 1984), could be used as another diagnostic measure of certain trace metals in natural water. The CuCC is acknowledged now as the total concentration of dissolved organic ligand, LT, which is associated with the fraction of the seawater DOM capable of forming stable metal compounds with the metal chosen to titrate the sample. In more general terms, the CuCs.C might also be considered as a 'seawater metal interaction capacity parameter', in which the eventual metal displacement reactions should be considered. Thus, the CuCC may simply be the principal component of a larger CuCs.C. However, more information is necessary on

Cu(ll )-ION SELECTIVEELECTRODE BEHAVIOUR

181

the nature of the structural chemical bonding of the metal-DOM interactions, to clarify whether the coordination is simple or chelation is involved. Our experiments indicate that Cu-ISE potentiometry, under conditions of super-Nernstian electrode behaviour, can be useful for simultaneously measuring the CuCs.C and the labile Ccu in surface coastal seawater. However, these gains pertain to filtered, unstirred, and constant pH sample solutions, which have been allowed to approach equilibrium in the region next to the electrode surface. Assays carried out in seawater subsamples contaminated with metallogenic wastes do not give the expected results. The principal problem of the method proposed here is the long equilibration time and therefore the potential loss of copper through surface adsorption, although natural waters enriched in humic materials are less exposed to loss of trace metals during storage (Heiden and Aikens, 1983 ). The electrode diffusive mechanism suggested would depend on the intrinsic 'adsorptive, complexing and reducing properties' of the seawater DOM. Thus, only an exceptionally strong cupric complexing ligand, but with a poor tendency to be adsorbed on the surface membrane electrode, would permit Nernstian electrode behaviour. The data presented in this paper indicate that this is unlikely to occur in seawater.
ACKNOWLEDGEMENT

This work was supported by FONDECYT/CONICYT Chile (grants 137/ 87 and 90/0600).

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