Notes References

ANDERSON, N. H., AND D. M. LEHXIKUHL. 1967. Catastrophic drift of insects in a woodland stream. Ecology 49 : 198-206. LAGLEFI, K. F. 1970. Freshwater fishery biology, 2nd ed. Brown. MENHINICK, E. F. 1964. A comparison of some species-individuals diversity indices applied to samples of field insects. Ecology 45 : 859-861. TEBO, L. B. 1955. Effects of siltation, resulting from improper logging, on the of a small trout stream in the palachians. Prog. Fish-Cult. 17: WATERS, T. B. 1964. Recolonization stream bottom areas by drift. Fish. Sot. 93: 311-315. Interpretation of 1965. -* Ecology 46 : drift in streams.

857
bottom fauna southern Ap64-70. of denuded Trans. Am. invertebrate 327-333.

Submitted: 2 April 1973 Accepted: 11 March 1974

Thermodynamic limitations in Eh measurements

on the use of the platinum

electrode

Abstract-The thermodynamic stability of surface oxide and sulfide coatings on the platinum electrode is considered. In well mixed environments thermodynamic considerations and experimental evidence suggest that the platinum surface acts as an oxide electrode that responds to pH rather than to oxygen partial pressure. In stagnant conditions in the marine or estuarine environment the slow formation of platinum sulfide may push the measured Eh values to more negative potentials if permanently emplaced electrodes are used. These reactions may restrict the operational use of Eh measurements.

Since the work of Gillespie (1920) the potential of the platinum electrode (Eh) has been widely used to characterize natural environments and on occasion to draw conclusions about the precise oxidation-reduction conditions within a particular system. Although it is now clear that such deductions are only valid in rather exceptional circumstances (Berner 1963; Bricker 1965; Hem 1961) there is still a considerable interest among biologists and geologists in the use of Eh as an operational parameter for mapping variations in the level of oxidative degradation in the field. This empirical application, originally suggested by ZoBell ( 1946)) h as received considerable circumstantial support from a variety of sources (Hewitt 1950; Sato 1960; Mortimer 1971; and others). The main physicochemical objections to the use of Eh as an operational parameter can be summarized as follows:

Experimental difficulties associated with the disturbance of the sample (release or absorption of gases, e.g. 02, H$ ) and reactions at the liquid junction of the reference electrode (precipitation of heavy metal sulfides, effect of suspended matter). Low exchange current densities at the platinum surface and the predominance of mixed potentials should give rise to instability and poor reproducibility in the measurements. The response of the platinum electrode to changes in the environment will depend to a large measure on the properties of the platinum surface and the presence of adherent surface coatings. It must be stressed that these are problems associated with the operational use of Eh. Additional problems arise if the Eh values are to be interpreted as oxidationreduction potentials (Morris and Stumm 1967; Stumm 1967; Whitfield 1969). However, if the objections raised above can be overcome-or at least understood in more detail-then the practical use of Eh values can proceed with greater confidence. In previous communications I have considered procedures for improving the quality of the experimental measurements (Whitfield 1969, 1971~) and for estimating the equilibrium exchange current densities at the platinum surface (Whitfield 1972). This paper will consider some facets of the final obstacle affecting Eh measurements -the properties of the platinum surface.

858
Table 1. Stability constants 25C and 1 -atm pressure. for reactions

Notes
involving platinum metal in natural aqueous solutions at

Reac tlon No.

Equation

(1)
(2) (3) (4) (5) (6)

pt" pt" pt" pt" pt"

+ H20 + H20 + 2H20 + 3H20 + 4H20

-,a -

'

Pt-0-k + 2H+ + 2ePtO -F 2H+ + 2ePt02 + 4H+ + 4ePtO. 2H20 + 2H+ + 2e-

-0.88 -0.9 -2.08 -1.00 -0.96

-29.73'

-30.4
-141

-33.8 -64.9 -66.3

-71.6

pt" + 5H20
pt" pt" + 6~~0 + 3H20

pto2. pto2.

3H20 + @I+ + 4e@I20 + @I+ + 4e-

-0.98 -1.06 -1.5

-1.6 -1.11

(7)
(8) (9) (10) 01) 02)

-4

Pto3 + 6H+ + 6ePto + 8~+ + 8ePt304 + 8~+ + 8ePt(OH)2 + 2H+ + 2ePt(OH)62PtS + 4H*o Ptcl + 6H+ + 4e-

-152
-216

pt" + @.I20
so pt" pt" pt" pt" pt" pt" + @I20 + 2H20

----A

-150
-33.1s

-0.98

(13)
(14) (15) (16)
*Calculated

+ 6H20 2+ 8~+ + 6e- \+ so

-97.555 52.0511 -24.7s -47.7s -qo.65

+ 401+ 601-

\ y -

2- + 2e-

PtC162- + 4ept2+ + 2e-

only for the formation

of adherent

oxide phases. rather than

tPt-0 represents a layer of adsorbed oxygen atoms on the platinum surface a layer of oxide, PtO (Hoare 1968: pa 34). Solid phases are underlined. $Data from Hoare (1968) unless otherwise stated.

De Bethune and Swendeman-Loud (1964).

IISee text. When Eh measurements are made, the platinum electrode is assumed to be an inert sensor providing a site for electron exchange (Whitfield 1971b). If the metal actually reacts with substances dissolved in the water then its properties will alter and it will display potentials that are characteristic of the electrode rather than of the environment. Here I will explore the consequences of direct attack of the platinum surface. It will then be possible to decide how far these fundamental processes support or militate against the use of Eh as an environmental parameter. The stability of various coatings on the platinum surface will be calculated from reversible thermodynamics. Since this form of analysis assumes that all reactions attain

Notes equilibrium, it results in an oversimplified picture of the state of the platinum surface. In practice kinetics will control the transition from one surface coating to another. At present it is not possible to consider in detail the influence of these rate processes in such complex aqueous media. Stability constants for the most important equilibria affecting the chemistry of the platinum surface are collected in Table 1. Data for the formation of platinum oxides and hydroxides were taken from the compilation of Hoare ( 1968, p. 19). This listing is more complete than other tabulations (Pourbaix 1966; Sillen and Martell 1964) and includes data on most of the phases that have been considered in electrochemical investigations of the platinum-oxygen system. Data for the dissolved phases were taken from DeBethune and SwendemanLoud ( 1964) and adjusted to refer to direct attack of the platinum metal. The relationship for the formation of PtS( s) was derived from the equations (DeBethune and Swendeman-Loud 1964)

859

PE

Fig. 1. Stability for platinum compounds in solutions where pH = 8.3, pC1 = 0.45, and pS0, = 2.47 at 25C and l-atm pressure. Numbers on the curves identify the equations in Table 1 that describe the formation of the various components, e.g. line 6 refers to the formation of PtO, * 3H,O.

(Sill& 1965). aos is the activity of the oxide or hydroxide phase and apt0 is the activity of the platinum metal. The correlog10 K sponding equations for the formation of zs PtS(s) + 2H++ 2e-= 11.05 Pt + H,S( aq) the sulfide and of the chloride complexes SOI'- + 10H + 8e- e H&(aq) + 4Hz0 = 41.0 are log (arts : al+) + pS04 + 8pH + 6pE = 52.05, (18) log (aPtCI,?-:apto) + 4pCland log (aPtC1,2-: arto) + 6pClwhere pCl = -logl,,acl etc. A plot of the activity ratio of complex to free metal [log (apti : apto) ] versus pE with given values of pH, pC1, and pS04 will indicate which complexes are predominant at different points in the pE range (Sillen 1959; Butler 1964). Since the stoichiometric numbers (x) for pH and pE are equal for each oxide phase (equation 17), the relative positions of the lines will not be altered by pH shifts and so a single activity ratio diagram can be used to select the oxide phases to be considered as stable coatings on the platinum surface over the entire pH range. 4pE = -47.7, (20) 2pE = -24.7, (19)

Pt + SOI- + 8H + 6e- e PtS(s) + 4H,O = 52.05

Since sulfate reduction is actually mediated by bacterial action and rarely runs to completion in the natural environment this equation will set a pessimistic upper limit for the onset of platinum sulfide formation. The stability constants used refer to infinite dilution. No attempt was made to correct for the effect of ionic strength (e.g. Stumm 1967; Dyrssen et al. 1968) since the corrections involved ( -+ 10%) will not materially affect the deductions drawn from the data; they will definitely be less than the uncertainties in the values of the stability constants used. For the formation of the oxides or hydroxides, the equilibrium relationships (equations l-11 : Table 1) can be written in the form log (aoX: aFto) - x(pH - pE) = log K; (17) pE (= -log,, a,-) corresponds to the oxidation power of the system at equilibrium

860

Notes is the dominant electron acceptor and the formation of an oxide phase on the surface of the platinum electrode has a significant influence on its behavior. Oxygen rapidly becomes adsorbed onto a fresh platinum surface at moderate oxygen pressures and the derma-sorbed layer, once formed, is difficult to remove (Hoare 1968). Furthermore there is evidence that oxygen actually dissolves in the bulk platinum and if the surface oxide layer is removed by cathodic stripping in a nitrogen-saturated solution then a new oxide coating is formed by diffusion from the body of the metal. Several monolayer equivalents of oxygen may be dissolved in the platinum so that even under conditions where the free platinum surface is thermodynamically stable, oxide coatings may still persist. Despite detailed investigations (e.g. Hoare 1968; Ives and Janz 1961) the nature of the oxide coat remains unresolved. According to Hoare (1968, p. 41) the definitive experiment is yet to be done to determine conclusively in what form the adsorbed oxygen on platinum exists. Peshchevitsky et al. (1967) have suggested that the formation of Pt ( OH) 2*xHzO phases might be predominant in controlling the potential of the platinum electrode in the natural environment. Stumm and Morgan (1970) suggest that the formation or decomposition of Pt ( OH) may give rise to spurious potentials in natural media. These suggestions would appear unlikely on the basis of the available thermodynamic data ( Fig. 1). Hoare ( 1968) noted specifically that Pt(OH) 2 was not considered in the interpretation of electrode potentials because it is very unstable under normal conditions. Most electrochemical investigations have suggested (as is borne out by Fig. 1) that the stable phases are probably Pt-0, PtO,, or various admixtures of these components. These coatings are electronically conducting, and, if the surface layer is intact, the platinum electrode should record the reversible oxygen potential according to the equation O2 + 4H+ + 4e- * 2H20 E" = 1.229 V. (21)

+8

PE

-8

4 P

Fig. 2. Predominance area diagram for platinum compounds on the pH-pE plane for solutions where pC1 = 0.45 and pSOI = 2.47. The vertical line corresponds to the conditions shown in Fig. 1. Broken line indicates the corresponding boundary in freshwater with pSOa = 3.92. The shaded area indicates conditions where water itself is unstable.

The diagram for seawater at pH 8.3 (Fig. 1) indicates that the solid phases PtS, Pt, Pt-0, and PtO, l 2H20 are stable over different spans of the pE range. Using this information we can construct a diagram which shows, on a pH/pE plane, the areas of predominance of the various phases (Fig. 2). The boundaries separating the stability regions can be obtained from equations 1, 5, and I3 by setting the ratios uos : uPtOand arts : aPta equal to one in equations 17 and 18 respectively. The stability boundaries for the formation of the chloride complexes (PtC1b2- and PtClG2-) can be obtained by setting the ratio aPtO:aPtCiX2-equal to unity in equations 19 and 20. These boundaries will be independent of pH (Fig. 2) but their position will depend on the chloride ion activity, shifting to higher pE values as pC1 increases. The anodic dissolution of platinum electrodes in acid chloride solutions is well documented (Frankenthal and Pickering 1965). In well aerated environments oxygen

Notes

861

Eh (VI

4
PH

Fig. 3. Predominance area diagram for platinum compounds ( Fig. 2 ) superimposed on the collected observations of Baas-Becking et al. (1960) for E/z/pH data in natural aqueous environments. Lines a, b, and d correspond to the boundaries shown in Fig. 2. Line c follows the irreversible oxygen potential (Merkle 1955). Vertical boundaries represent pH barriers as discussed in the text. The position of the stability boundaries for the chloride complexes are for solutions where pC1 = 0.45. Region A includes measurements made in well mixed environments where the oxygen partial pressure is high. Region B contains data from stagnant environments where oxygen has been replaced by other electron acceptors.

862

Notes

The electrode potential . would then respond to changes in the oxygen partial pressure. The contribution of this reaction will however be negligible unless impurities are rigorously removed from the solution. When the impurity concentration approaches 10-lOM the exchange current density of the reversible oxygen electrode is already being swamped (Bockris and Reddy 1970). In natural media one would expect the platinum electrode to act primarily as an oxide electrode, measuring PH. This suggestion, which has also been discussed by Peshchevitsky et al. ( 1967)) is most conveniently checked by considering the data of Baas-Becking et al. (1960) who collected over 4,000 Eh/pH readings and used them to delineate chemically distinct environments. Although their detailed boundaries might appear rather speculative in the light of the more recent work of Stumm ( 1967) and Sillen (1965), their paper contains the most comprehensive survey of empirical Eh values to date. The readings they record cover most of the Eh/pH span available, but more than 90% of their data on natural aqueous environments lies within a fairly restricted area (Fig. 3). At high Eh values (region A, Fig. 3) the platinum electrode exhibits a pH-sensitive response that is described quite accurately by the equation summarizing the function of the Pt-0 coated electrode as a pH electrode: E = Eopt,rt.O - 0.06pH [ E~~t,pt~O 0.88 V] . = The bulk of the readings fall within k-53 mV of this line ( Fig, 3, line b) . This same equation was attributed by Peshchevitsky et al. (1967) to the pH function of 2H20 on the platinum surface. Pt( OH)a The calculated E value is similar to that observed experimentally by Baas-Becking et al. (1960: E = 0.81 V) and by Cooper (1937: E = 0.846 V) in oxygenated solutions at various pH values. These E values are also close to that for the peroxide reaction (Ives and Janz 1961).
l

Fig. 4. Stability diagrams analogous to Fig. 1 for the other platinum group metals with pH = 8.3. Only the stable phases are shown for clarity. Data to *construct the diagram were taken from Hoare ( 1968). The stable phases identified were ( reading from the high pE phase in each case ) OsOa; RuOz; IrOz, Ir203, Ir-0; I&03, Rh-0; PtO, .2H20, Pt-0; PdO.

H202 + e- = OH + OH-

E = 0.835 V.

This agreement must be considered coincidental unless it can be shown that the necessary concentrations of peroxide ( > 10~~M) exist in the natural environment. The corresponding equations for the PtO,* 2H20 oxide electrode (E = 0.96 V: line a, Fig. 3) and for the so-called irreversible oxygen electrode (E = 0.70 V: line c, Fig. 3: Merkle 1955; Garrels and Christ 1965) appear to set upper and lower limits to this pH function but cannot be considered of the bulk of the data representative points. The other noble metals (Rh, Ir, Pd, Ru, OS) form similar oxide coats and are liable to show pH functions with E values close to that of platinum under the same conditions (Fig. 4). Gold does not form a stable oxide coating but it is characterized by very small exchange currents in the natural environment (Whitfield 1972) and does not give a useful Eh electrode. The data points shown in region A ( Fig. 3) were taken exclusively in environments where the oxygen partial pressure is high and include

Notes normal soils, shallow groundwater, seawater, and river water. Meteoric waters account for most of the readings on the acid side of the pH 6 boundary. Under these circumstances the platinum electrode will not respond to changes in the partial pressure of oxygen. The Eh value will therefore not give any indication of the oxidation-reduction status of the system unless other electroactive couples are present in sufficient concentration ( > 10e5M) to dominate the electrode potential (Peshchevitsky et al. 1967; Bohn 1968). There is evidence to suggest that iron (Hem 1961) and manganese ( Bricker 1965) couples may occasionally act in this way. From the operational point of view the consequence of the oxide electrode function of the platinum surface is to associate large, positive Eh values with well aerated systems. If we exclude meteoric waters the Eh values for such systems should range from +500 mV to +300 mV. Readings represented in region B (Fig. 3) reflect the behavior of the platinum electrode in stagnant environments where oxygen has been replaced by other electron acceptors. This region includes measurements made in freshwater lakes, evaporite basins, and in the interstitial waters of freshwater, marginal marine, and open-sea sediments. The vertical boundaries of region B in Fig. 3 reflect the importance of the carbon dioxide system in buffering the pH of isolated or stagnant environments. The buffering capacity of the carbon dioxide system is at a maximum when pH = pKi and pH = p&, where pK1 and pK2 are the negative logarithms of the first and second acidity constants respectively of the carbon dioxide system. The relevant values at 25C are pH 6.4 and 10.4 in freshwaters and pH 6.0 and 9.2 in seawater (Stumm and Morgan 1970). Pytkowicz ( 1967) has convincingly demonstrated the role of the carbon dioxide system in buffering the oceans against changes in pH over periods of thousands of years. If this mechanism is accepted then the pH of natural systems will tend to vary around the buffer intensity minimum for the carbon

863

dioxide system between the peaks at pH = pK1 and pH = pK,. In all but the softest waters the pH will rarely rise above 9.5 because of the onset of precipitation of calcium and magnesium carbonates. In region B (Fig. 3) the platinum electrode is no longer responding primarily to pH. Either the formation of the oxide coating is precluded by the low pE values experienced as oxidative degradation proceeds-as is suggested by the thermodynamic evidence-or else the platinum surface is responding to other redox systems -either as mixed potentials, reaction potentials, or redox potentials. There is evidence to suggest that the platinum electrode is responsive to changes in the status of the nitrogen (Bailey and Beauchamp 1971)) iron ( Doyle 1968), and sulfur (Berner 1963) systems as oxidative degradation proceeds. The incomplete oxide coating which probably still persists, despite the increasing stability of the clean platinum surface, will not hinder these other reactions since it is electronically conducting and able to transmit the effects of surface reactions to the bulk metal. However, at low pE values platinum sulfide becomes the stable phase (see also Najdeker and Bishop 1973) and this might present a lower limit to the usefulness of the platinum electrode. In reduced systems containing sulfur it has been shown over a wide geographical range (Berner 1963; Skopintsev et al. 1966; Whitfield 1969) that the platinum electrode responds to the potentials established by the system HS-(aq) + SO(rhomb.) + H+ + 2em. This is equivalent for which Eh = -0.485 + 0.0295 pS. We can rewrite the equation for the formation of platinum sulfide in a similar form so that Pt + S2- * PtS + 2e- log K = 32.05 for which Eh = -0.96 + 0.0295~s. to the half cell S2- * So(rhomb.) + 2 e-,

864

Notes ions has been confirmed by observations in sulfur-bearing muds and a correlation in sign and magnitude has been confirmed between the potentials observed and those predicted by the thermodynamic equations. These points taken together indicate that the operational use of Eh measurements may be restricted to region B of Fig. 3. M. Whitfield The Laboratory Citadel Hill Plymouth PLl 2PB England References
BAAS-BECXING, L. G. M., I. R. KAPLAN, AND D. MOORE. 1960. Limits of the natural environment in terms of pH and oxidationreduction potential. J. Geol. 68: 243-284. BAILEY, L. D., AND E. G. BEAUCHAMP. 1971. Nitrate reduction and redox potentials measured with permanently and temporarily placed platinum electrodes in saturated soils. Can. J. Soil Sci. 51: 51-58. BERNER, R. A. 1963. Electrode studies of hydrogen sulfide in marine sediments. Geochim. Cosmochim. Acta 27: 563-575. BOCKRIS, J. OM., AND A. K. N. REDDY. 1970. Modem electrochemistry, v. 2. McDonald. BOHN, M. L. 1968. Electromotive force of inert electrodes in soil suspensions. Soil Sci. Sot. Am. Proc. 32: 211-215. BRICKER, 0. P. 1965. Some stability relations in the system Mn-OrHzO at 25C and one atmosphere total pressure. Am. Mineral. 50: 1296-1354. BUTLER, J. N. 1964. Ionic equilibrium, a mathematical approach. Addison-Wesley. COOPER, L. H. N. 1937. Oxidation-reduction potential in sea water. J. Mar. Biol. Assoc. UK. 22: 167-176. DE BETHTJNE, A. J., AND N. A. SWENDEMAN-LOUD. 1964. Standard aqueous electrode potentials and temperature coefficients at 25C. Hampel. 1968. The origin of the ferrous DOYLE, R. W. ion-ferric oxide potential in environments containing dissolved ferrous iron. Am. J. Sci. 266: 840-859. DYRSSEN, D., D. JAGNER, AND F. WENGELIN. 1968. Computer calculation of ionic equilibria and titration procedures. Almqvist and Wiksell. FRANKENTHAL, R. P., AND H. W. PICKERING. 1965. Some considerations on the use of platinum electrodes in chloride solutions. J. Electrothem. Sot. 112: 514-517.

Therefore one would expect the attack of the platinum surface by sulfide to be accompanied by a relatively sharp drop in Eh. Apparently the rate of attack is slow and the experience of Hayes et al. (1958) is typical. They left a platinum electrode overnight in sulfide-bearing mud and found that the potential had drifted downward by 0.36 V. This result is of the same order as the predicted drop of 0.47 V. The electrode, when removed from the mud, had a distinct amber tarnish that was difficult to remove even under extremely oxidizing conditions ( coned nitric acid). The slowness of the tarnishing reaction and the direction of drift in potential were also confirmed by Baas-Becking et al. (1960). A thermodynamic analysis of the behavior of the platinum electrode over the pE/pH range of the natural environment indicates that the metal is susceptible to attack with the formation of oxides in the high pE range and platinum sulfide in the low pE range. The predictions of this analysis are borne out by a consideration of the trends in the Eh/pH data accumulated by Baas-Becking et al. ( 1960). The platinum electrode appears to be acting as an oxide electrode in well aerated systems and it responds to pH in a manner analogous to that predicted for the Pt-0 electrode. It is, however, insensitive to changes in the oxygen partial pressure. In the intermediate region where the thermodynamic analysis predicts that free platinum is stable, the surface of the electrode is still likely to be coated with oxide since the rate of release of oxygen by the platinum is very slow compared to the reading times normally used in fieldwork. The behavior of the electrode in this region has been inadequately studied, although it has been shown that under restricted circumstances the electrode may respond to redox reactions in the manganese, iron, nitrogen, and sulfur systems. These reactions, where they are established, continue the hierarchy of decreasing Eh values with the progressive oxidative degradation of organic matter. The attack of the platinum by bisulfide

Notes
CARRELS, R. M., AND C. L. CHRIST. 1965. Solutions, minerals and equilibria. Harper and Row. GILLESPIE, L. J. 1920. Reduction potentials of bacterial cultures and of waterlogged soils. Soil. Sci. 9: 199-216. HAYES, F. R., B. L. REID, AND M. L. CAMERON. 1958. Lake water and sediment. 2. Oxidation-reduction relations at the mud water interface. Limnol. Oceanogr. 3 : 308-317. HEM, J. D. 1961. Stability field diagrams as aids in iron chemistry studies. J. Am. Water Works Assoc. 53: 211-232. HEWITT, L. F. 1950. Oxidation-reduction potentials in bacteriology and biochemistry, 6th ed. Livingstone. HOARE, J. P. 1968. The electrochemistry of oxygen. Wiley. IVES, D. J. G., AND G. J. JANZ. 1961. Reference electrodes. Theory and practice. Academic. MERKLE, F. G. 1955. Oxidation-reduction processes in soils, p, 200-218. In F. E. Bear [ed.], Chemistry of the soil. Am. Chem. Sot. Monogr. 126. MORRIS, J. C., AND W. STUMM. 1967. Redox equilibria and measurements of potentials in the aquatic environment. Adv. Chem. Ser. 67. MORTIMER, C. H. 1971. Chemical exchanges between sediments and water in the great lakes-speculations on probable regulatory mechanisms. Limnol. Oceanogr. 16: 387404. NAJDEKER, E., AND E. BISHOP. 1973. The formation and behaviour of platinum sulphide on platinum electrodes. J. Electroanal. Interfacial Electrochem. 41: 79-87. PESHCHEVITSKY, B. E., N. M. NIKOLAEVA, AND B. A. VOROTNIKOV. 1967. The limits of application of smooth platinum electrodes in measuring Eh of natural waters. Geol. Geofiz.

865

the buffer mechanism of recent oceans. Geochim. Cosmochim. Acta 31: 63-73. Oxidation of sulphide ore SATO, M. 1960. environments in bodies. 1. Geochemical terms of Eh and pH. Econ. Geol. 55: 92% 961. 1959. Graphic presentation of SILLiN, L. G. In I. M. equilibrium data, p. 277-317. Kolthoff and P. J. Elving [eds.], Treatise on analytical chemistry, part 1, v. 1. Interscience. -. 1965. Oxidation state of the earths ocean and atmosphere. 1. Arkiv Kemi 24: 431-456. 1964. Stability -, AND A. E. MARTELL. constants of metal-ion complexes. Chem. SOC. ( Lond. ) Spec. Publ. 17. SKOPINTSEV, B. A., N. N. RO~NSKAYA, AND E. V. SMIRNOV. 1966. New determinations of the oxidation-reduction potential in Black Sea Water. Oceanology 6: 653-659. 1967. Redox potential as an enSTUMM, w. conceptual signifivironmental parameter; cance and operational limitation. Adv. Water Pollut. Res. 1: 283-307. -, AND J. J. MORGAN. 1970. Aquatic chemistry. Wiley-Interscience. Eh as an operational 1969. WHITFIELD, M. Limnol. parameter in estuarine studies. Oceanogr. 14: 547-558. 1971a. A compact potentiometric sen-. In situ determination of sor of novel design. pH, pS, and Eh. Limnol. Oceanogr. 16: 829-837. -. 1971b. Ion selective electrodes for the Aust. Mar. Sci. analysis of natural waters. Assoc. -. 1972. The electrochemical characteristics of natural redox cells. Limnol. Oceanogr.

17: 383-393.
ZOBELL, C. E. 1946. Studies on redox potential of marine sediments. Bull. Am. Assoc. Petrol. Geol. 30: 477-513.

1967(g): 32-40.
POUFIBAIX, M. J. N. Atlas of electro1966. chemical equilibrium in aqueous solutions [ transl. by J. A. Franklin]. Pergamon. PYTKOWICZ, R. M. 1967. Carbonate cycle and

Submitted: Accepted:

25 October 1973 28 February 1974