Aquatic Geochemistry 5: 227248, 1999. 1999 Kluwer Academic Publishers. Printed in the Netherlands.

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EH, pH Diagrams for Mn, Fe, Co, Ni, Cu and As under Seawater Conditions: Application of Two New Types of EH, pH Diagrams to the Study of Specic Problems in Marine Geochemistry
GEOFFREY P. GLASBY and HORST D. SCHULZ
Universitt Bremen, Fachbereich Geowissenschaften, Postfach 330 440, D-28334 Bremen, Germany (Accepted 8 January 1999) Abstract. EH , pH diagrams have been calculated using the PHREEQC programme in order to establish the predominance elds of Mn, Fe, Co, Ni, Cu and As in bottom waters from the Angola Basin. Predominance elds are presented separately for both aquatic species and solid mineral phases in order to simplify interpretation of the data. The diagrams show signicant differences from standard EH , pH diagrams for these elements calculated for freshwater at 25 C and 1 bar which assume an element concentration of 106 M. In particular, our diagrams show that Mn2+ and NiCO0 are 3 the predominant aquatic species for Mn and Ni in bottom seawater and FeOOH, Fe2 O3 , Fe3 O4 , CoFe2 O4 , CuFe2 O4 , CuFeO2 , and Ba3 (AsO4 )2 the predominant solid phases for Fe, Co, Cu and As, respectively. Mn and Ni are therefore undersaturated and Fe, Co, Cu and As supersaturated in bottom seawater from the Angola Basin. Neither rhodochrosite (MnCO3 ) nor siderite (FeCO3 ) can form in this marine environment in equilibrium with seawater. A mixed Mn-Ca carbonate is therefore formed within the pore waters of reducing sediments. The high Ni/Cu ratios in cobalt-rich manganese crusts formed adjacent to the oxygen minimum zone may be explained by the change from Cu2+ to CuCl2 as the dominant aquatic species of Cu in seawater at an EH of +0.48 V. 3 Key words: EH , pH diagrams, seawater

1. Introduction EH , pH diagrams have been in use for more than 30 years (Garrels and Christ, 1965) and have played an important role in understanding marine geochemical processes. Brookins (1988) performed a valuable service in preparing such diagrams for 75 elements. Unfortunately for the marine geochemist, these diagrams were calculated for natural waters at 25 C and 1 bar, generally assuming an element concentration of 106 M. We have therefore computed these diagrams for a number of key elements under seawater conditions using element concentrations prevalent in the deep waters of the Angola Basin as an example. The aim of this paper is to see if there are any signicant differences between these new EH , pH diagrams and those presented by Brookins (1988) and, if so, to assess their geochemical implications.

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Calculation of the EH , pH diagrams presented here involved the use of PHREEQE, a computer programme initially developed by Parkhurst et al. (1980, 1990) and later modied by Klling (1992). Subsequently, Parkhurst (1995) substantially revized and amended this programme to produce a new version PHREEQC in order to eliminate many of the deciencies and limitations in PHREEQE. We have used this new version which includes revized datasets of thermodynamic constants in the calculations presented here. Unfortunately, no data were available for Co in PHREEQC. Calculations for Co were therefore made with PHREEQE using thermodynamic data from the EQ3/EQ6 thermodynamic data set (Wolery, 1992). One problem with these calculations is that so much information is produced that it is no longer realistic to present all the data for each element on a single EH , pH diagram. It was therefore decided to split the data to show the relations between the various aquatic species and those between the various minerals which are predicted to be supersaturated in the associated solutions. These results are then presented in individual diagrams side by side which clearly show that the aquatic species and the solid mineral phases with which they coexist are initially independent of each other. This challenges the implicit assumption of EH , pH diagrams that aquatic species cease to exist at the boundary where solutions become supersaturated with respect to an associated mineral phase. Supersaturation does not necessarily mean precipitation and solutions can be supersaturated with respect to more than one mineral. In addition, the stability elds of related solid phases which very often overlap are shown because the precipitation of solid phases is often controlled by kinetic rather than thermodynamic factors. We believe that these diagrams therefore represent a more realistic statement of the geochemistry of individual elements than the more traditional EH , pH diagrams. The concentration data used to calculate these diagrams were based on measured seawater concentrations for bottom water from the Angola Basin and the temperature was taken to be 2 C. However, the diagrams were calculated at one atmosphere pressure and no correction was applied for pressure. These data are summarized in Table 1. For the solid phases, only oxides, hydroxides, sulphides and carbonates were considered in these calculations. About 2000 points were used in the calculation of each of these diagrams with repeat calculations made at distances in pH of 0.10.2 pH and in EH of 0.020.05 V. Nonetheless, some parts of the diagrams are not very meaningful such as those corresponding to pH values <4 and >9. However, the results calculated by PHREEQC represent the most modern and complete set of thermodynamic data available for equilibrium constants and saturation equilibrium constants for individual species. In our interpretation of these diagrams, we have assumed an Eh of +0.4V and a pH of 8 for seawater. These are the values normally given in the literature (Garrels and Christ 1965, Fig. 11.2; Brookins 1988, Fig. 1).

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Table I. Listing of the various parameters (density, temperature and element concentrations) used in the calculation of the EH , pH diagrams in seawater. Data for deep seawater taken from our own analyses in the Angola Basin. Concentrations of Cu, Ni, As, Zn and Co taken from Bruland (1983). Density (mg mm3 ) Temp. ( C) Ca (ppm) Mg (ppm) Na (ppm) K (ppm) Si (ppm) Cl (ppm) C (ppm) S (ppm) N (ppm) P (ppm) F (ppm) Sr (ppm) Fe (ppb) Mn (ppb) Cu (ppb) Ni (ppb) As (ppb) Ba (ppb) Zn (ppb) Only in use with PHREEQE: Co (ppb) 1.023 2.0 427 1 284 10 760 390 7.8 19 350 36.4 2 600 2.5 0.2 1.1 7.1 0.021 0.012 0.38 0.0017 1.7 0.02 0.52

As SiO2 As C As SO2 4 As NO 3 As PO3 4

As Cu As As

0.4

There were several reasons why two separate EH , pH diagrams are required to show the distribution of aquatic species and the saturation of minerals. Although the denition of the boundary for aquatic species is quite clear and the species with the highest concentration is always shown, aquatic species also occur where minerals are supersaturated. Where several minerals are involved, the degree of supersaturation becomes greater and less space is available to show the distribution of the aquatic species. A single EH , pH diagram therefore becomes too complex. In addition, many minerals are supersaturated in parts of the diagram. Supersaturation does not necessarily lead to the precipitation of the mineral, only the possibility of precipitation. The solid phase diagrams show lines where the degree of saturation for each mineral is zero. Minerals with the same constituents but different free en-

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ergies of formation such as MnO2 have lines which are close together and parallel to one another because they are calculated using the same precipitation/dissolution reactions but with different equilibrium constants. The EH , pH diagrams presented here are specic for the deep ocean waters of the Angola Basin. They are not generally valid for all marine systems. For each specic situation, a new EH , pH diagram must be calculated. The calculation of these diagrams depends on the thermodynamic dataset used, in this case the most recent version of PHREEQC (Parkhurst, 1995; available on the internet http://wwwbrr.cr.usgs.gov/projects/GWC coupled/). This dataset is comparable with the WATEQ4 and MINEQL datasets which are also available in the PHREEQC format on the same web site. Each of these three datasets uses the most recent thermodynamic data and may be considered state of the art. Of course, the calculated diagrams present only equilibrium relationships and do not consider reaction rates or pathways. It is the decision of the author which mineral phases are displayed. In general, these are chosen to address a specic scientic question, in this case the formation of deep-sea manganese nodules. Only a limited area on the EH , pH diagram is relevant to this specic problem. This choice of topic led us to consider six elements relevant to the study of the deposition of the ferromanganese oxide phases and the uptake of the various metals in the deep sea (Glasby, 1999). Co was chosen because it has two principal modes of uptake into the ferromanganese oxide phase, either in the divalent or trivalent state. Ni and Cu are taken up dominantly in the divalent state but Cu is of particular interest because of its known depletion in Co-rich manganese crusts taken below the oxygen minimum zone. As is of interest because it is an anionic species in seawater which is taken up in deep-sea manganese nodules predominantly in the iron oxyhydroxide phase. Self evidently, these diagrams are not valid for sulphide formation in anoxic basins where element concentrations are at least an order of magnitude higher than those considered here. In particular, two diagrams were prepared for each element because too much information is generated for one diagram. These diagrams may be considered to be predominance diagrams, that is they show the predominant species present at each point on the diagram. For the solid phases, the diagrams may also be considered to be saturation diagrams. Each aquatic species is, in principle, present throughout the diagram, albeit in vanishingly small concentrations in some cases. In calculating these EH , pH diagrams, we consider only inorganic aqueous species as is standard practice. It is known that a signicant proportion of each element is present as organic complexes in seawater and, more particularly, in sediment pore waters. However, this situation has only a minor inuence on the predominance elds of the remaining inorganic aqueous species and affects the saturation boundaries of the solid phases only slightly. One signicant conclusion to emerge from this study is the need to calculate specic EH , pH diagrams in order to answer specic scientic questions about the conditions under which mineral formation/dissolution take place in the marine environment.

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3. Results The calculated EH , pH diagrams for Mn, Fe, Co, Ni, Cu and As are presented in Figures 16. They show signicant differences from those presented by Brookins (1988). For Mn, Mn2+ is the principal aquatic species of Mn in seawater as suggested by Hem (1972), Brookins (1988), Gramm-Osipov et al. (1991) and Gammons and Seward (1996). MnCO0 becomes the predominant aqueous species at pH values 3 >9.1 but MnCl+ is never a predominant species as indicated by Bruland (1983). In the solid phase, various MnO2 phases and MnOOH appear to be stable. This contrasts with the of nding of Brookins (1988) that the main solid phases are MnO2 , MnO and Mn3 O4 . MnO2 , one of the principal minerals occurring in deepsea manganese nodules, has a standard free energy of 108.9 kcal/mole (Bricker 1965). It can be shown that the stability boundary for MnO2 has the same gradient as the boundaries for nsutite and pyrolusite and lies between these two lines. Nonetheless, these solid Mn oxyhydroxide phases are not thermodynamically stable under deep sea conditions. Rhodochrosite (MnCO3 ) does not occur as a stable solid phase. The formation of MnS requires high activities of dissolved sulphide and Mn coupled with a low activity of Fe (Bttcher and Huckriede, 1997). The predominance eld of MnS therefore lies outside the predominance diagram of Mn presented here. For Fe, Fe(OH)0 is the principal aquatic species in seawater. FeCl2+ , FeSO+ , 3 4 FeF2+ , Fe(OH)+ and Fe(OH) are the other preferred forms of Fe in the trivalent 2 4 state and Fe2+ in the divalent state. The species identied here are the same as those indicated by Bruland (1983) to predominate in seawater (Fe(OH)0 , Fe(OH)+ and 3 2 Fe2+ ) with the exception of FeCl+ which is not observed. Fe(HS)0 and Fe(HS) are 2 3 the stable aqueous species under reducing conditions. Goethite (-FeOOH), maghemite ( -Fe2 O3 ) and magnetite (Fe3 O4 ) appear to be the stable solid phases under deep-sea conditions. Pyrite is the stable solid phase under reducing conditions but siderite (FeCO3 ) appears to be undersaturated in seawater. For Co, Co2+ is the principal aquatic species in seawater. CoCO and CoCl+ 3 do not appear to be dominant species as indicated by Bruland (1983). Cosovic et al. (1982) established the dominant form of Co in seawater to be Co2+ with lesser amounts of CoSO0 and CoCl+ and minor amounts of CoOH+ , Co(OH)0 4 2 and CoCO0 based on polarographic studies but these additional species are not 3 predominant on this diagram. CoFe2 O4 appears to be the stable solid phase under seawater conditions. This differs from the ndings of Brookins (1988) that Co3 O4 is the stable solid phase at the EH and pH of seawater with CoCO3 stable under slightly less oxidizing conditions and of Hem et al. (1985) that CoOOH is the stable solid phase at the EH and pH of seawater. For Ni, NiCO0 is the principal aquatic species in seawater and not Ni2+ as 3 indicated by Bruland (1983) and Brookins (1988). NiCl+ is also not predominant. All solid phases appear to be undersaturated in seawater.

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Figure 1. EH , pH diagrams the aquatic species and solid phases of Mn calculated for deep-seawater conditions in the Angola Basin (Table 1). The solid phases shown in the diagram are nsutite ( -MnO2 ), birnessite (Na0.7 Ca0.3 Mn7 O14 2.8H2 O but calculated from the data set as MnO2 ), pyrolusite (-MnO2 ), bixbyite (-Mn2 O3 ), hausmannite (Mn3 O4 ) and manganite ( -MnOOH).

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Figure 2. EH , pH diagrams the aquatic species and solid phases of Fe calculated for deep-seawater conditions in the Angola Basin (Table 1). The solid phases shown in the diagram are goethite (-FeOOH), hematite (-Fe2 O3 ), magnetite (Fe3 O4 ), maghemite ( -Fe2 O3 ), mackinawite (Fe9 S8 but calculated from the data set as FeS) and pyrite (FeS2 ).

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Figure 3. EH , pH diagrams the aquatic species and solid phases of Co calculated for deep-seawater conditions in the Angola Basin (Table 1). The solid phases shown in the diagram are cattierite (CoS), linnaeite (Co3 S4 ) and Co-spinel (Co3 O4 ).

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Figure 4. EH , pH diagrams the aquatic species and solid phases of Ni calculated for deep-seawater conditions in the Angola Basin (Table 1). The solid phase shown in the diagram is millerite (NiS).

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Figure 5. EH , pH diagrams the aquatic species and solid phases of Cu calculated for deep-seawater conditions in the Angola Basin (Table 1). The solid phases shown in the diagram are cupric ferrite (CuFe2 O4 ), cuprous ferrite (CuFeO2 ), chalcopyrite (CuFeS2 ), chalcocite (Cu2 S), covellite (CuS) and cuprite (Cu2 O).

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Figure 6. EH , pH diagrams the aquatic species and solid phases of As calculated for deep-seawater conditions in the Angola Basin (Table 1). The solid phases shown in the diagram are realgar (AsS) and orpiment (As2 S3 ).

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For Cu, CuCl2 and Cu(OH)2 are the principal aquatic species in seawater but 3 Cu2+ becomes the dominant species at an EH above +0.48 V. This differs from the ndings of Bruland (1983) that the principal forms of Cu in seawater are CuCO0 , 3 CuOH+ and Cu2+ . Cupric and cuprous ferrite (CuFe2 O4 and CuFeO2 ) are the oversaturated solid phases under deep-sea conditions. Various sulphides occur under reducing conditions. This contrasts with the diagram of Brookins (1988) which shows that the stable solid form of Cu at the EH and pH of seawater is CuO and ignores the occurrence of CuCl2 as an aquatic species. 3 For As, HAsO2 is the principal aquatic species in seawater. H3 AsO0 becomes 3 4 stable under more reducing conditions. Ba3 (AsO4 )2 is the dominant solid phase under deep-sea conditions. In the above diagrams, Mn and Ni are thermodynamically stable in the aqueous phase in under deep sea conditions demonstrating that the solid phases are undersaturated and Fe, Co, Cu and As in the solid phase demonstrating that the solid phases are supersaturated.

4. Discussion The validity of EH , pH diagrams is, of course, dependent on the thermodynamic data from which they were calculated. This is a problem in most natural environments where many solid phases are ne grained, non stoichiometric and impure. The use of themodynamic data for crystalline, pure solids is therefore not strictly accurate. This is particularly true for the solid phases of Mn and Fe, MnOOH, MnO2 and goethite, reported here (Giovanoli, 1980; Giovanoli and Arrhenius, 1988). This problem has been discussed by Glasby (1974), Gramm-Osipov et al. (1984) and Skinner and Fitzpatrick (1992). For Mn, there are a number of defect oxides. The occurrence of cryptocrystalline oxides suggests that these deposits have lower nucleation energies or lower free energies of formation than the more crystalline oxides (Burns and Burns, 1979), although the differences in free energy are small. Accurate thermodynamic data for these oxides are virtually impossible to obtain (Burns and Burns, 1979), although they are available for MnO2 (Bricker, 1965). For Fe, goethite (-FeOOH) is the thermodynamically most stable Fe oxyhydroxide mineral under seawater conditions (Gramm-Osipov et al., 1984; Waychunas, 1991; Schwertmann and Fitzpatrick, 1992) but ferrihydrite (FeOOH) (Murad and Schwertmann, 1988; Puteanus et al., 1991) or akagenite (-FeOOH) (Johnston and Glasby, 1978; Murray, 1979; Chen and Yao, 1995) are more likely to occur in marine minerals because of kinetic factors. However, thermodynamic data are not available for these minerals. Thermodynamic equilibria are, of course, dependent on temperature. In supercritical, hydrothermal uids, Mn and Fe are transported in the form of MnCl and FeCl (Uchida et al., 1995) (cf. Gammons 3 3 and Seward, 1996). This would facilitate the migration of Mn and Fe in submarine hydrothermal uids.

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For Mn, the role of MnOOH in formation of Mn oxides has long been known. For example, Bricker (1965) showed that MnOOH was precipitated rst on oxidation of Mn2+ and then immediately oxidized giving the appearance of direct precipitation to the more highly oxidized phase (cf. Grill, 1982; Pokrovskiy and Savenko, 1995; Gramm-Osipov, 1997). The MnOOH present in the marine environment is probably feitknechtite (MnOOH) (Hem and Lind, 1983; Hem et al., 1989). However, the reaction pathway proposed by Giovanoli (1980) does not show MnOOH as an intermediate in the formation of marine manganese nodules as does that of Bricker (1965). Crerar et al. (1980) pointed out that Mn(III) is unstable with respect to Mn(II) and Mn(IV) and therefore considered that Mn is present in feitknechtite as Mn(II) and Mn(IV) in equal amounts (cf. Gramm-Osipov et al., 1992). However, new evidence suggests that Mn in MnOOH is present mainly as Mn (III) (Murray et al., 1985; Manceau et al., 1992; Junta and Hochella, 1994). From the EH , pH diagram, Mn appears to be undersaturated in seawater with respect to MnOOH (cf. Crerar and Barnes, 1974). The phases precipitated on the seaoor may therefore be more stable than those prepared in the laboratory on account of their ne grain size and uptake of trace metals (Glasby, 1974). On kinetic grounds, it is known that efcient surface catalysis or microbial mediation is required for Mn2+ to be oxidized to MnO2 on a realistic time scale (Diem and Stumm, 1984; Tebo et al., 1997). Burns and Burns (1977) have demonstrated the role of FeOOH in initiating the deposition of Mn oxides in the marine environment. Autocatalytic oxidation on Mn oxides then becomes more rapid (Stumm and Morgan, 1970). For Fe, goethite is the stable phase at the redox conditions of seawater. This would account for the fact that Fe is present in seawater in both the particulate and soluble form (Bruland et al., 1994). Because of their different stability elds, FeOOH is less readily mobilized but more readily precipitated than MnO2 in the marine environment (Crerar and Barnes, 1974; Davison, 1993). This means that Mn is more mobile than Fe in both submarine hydrothermal (Hannington and Jonasson, 1992; Lilley et al., 1995) and shallow marine (Glasby et al., 1997) environments. These diagrams show that neither rhodochrosite (MnCO3 ) nor siderite (FeCO3 ) can form in the marine environment in equilibrium with seawater. However, as shown by Berner (1981), rhodochrosite does occur in both anoxic sulphidic and non-sulphidic environments whereas siderite is restricted to marine and non-marine anoxic non-sulphidic methanic environments. In fact, both these minerals are restricted to rapidly-accumulating, ne-grained, organic-rich sediments where CO2 is produced as a result of oxidation of organic matter, in part by Mn and Fe oxyhydroxides (Robbins and Callender, 1975; Emerson, 1976; Murray et al., 1978; Suess, 1979; Balzer, 1982; Manheim, 1982; Rper, 1988; Bruno et al., 1992; Huebner et al., 1992; Davison, 1993; Schulz et al., 1994; Thamdrup et al., 1994; Torres et al., 1995). Such sediments are characterized by high alkalinities and high dissolved Mn(II) and Fe(II) contents. In some cases, anoxic pore waters taken several

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metres below the sediment-water interface can have alkalinities nearly two orders of magnitude higher than in the overlying seawater (Schulz et al., 1994). In most cases, a mixed MnCa carbonate rather than pure rhodochrosite is formed (Suess, 1979; Manheim, 1982; Pedersen and Price, 1982; Middelburg et al., 1987; Aller and Rude, 1988; Jakobsen and Postma, 1988; Okita et al., 1988; Okita and Shanks, 1992; Calvert and Pedersen, 1993; Salonen et al. 1995; Huckriede and Meischner, 1996, Carman and Rahm, 1997; Friedl et al., 1997; Sternbeck and Sohlenius, 1997; Bttcher, 1998). Pure rhodochrosite can not form within marine sediments because the compositions of the pore waters do not lie within a range in which they would be in equilibrium with pure rhodochrosite (Middelburg et al., 1987). Unfortunately, no thermodynamic data are available for the mixed Ca MnCO3 . Calvert and Pedersen (1993) concluded that CaMnCO3 is precipitated from the interstitial waters of sediments rather than the overlying seawater since the aqueous Mn concentrations must be ve orders of magnitude higher than those in oxic sea water for CaMnCO3 to form. Only there would the Mn concentration be high enough to exceed the solubility product of MnCO3 (20120 mole/l) (Pedersen and Price, 1982). However, this calculation overestimates the concentration of Mn required since it is the thermodynamically more stable CaMnCO3 rather than the pure MnCO3 which precipitates. The precipitation of CaMnCO3 was assumed to occur only when the bottom sea water is oxic because only then can the surface sediments accumulate Mn oxyhydroxides to supply the Mn to be enriched in the interstitial waters of subsurface sediments on burial (Calvert and Pedersen,1993). These authors therefore proposed that the presence of Ca MnCO3 can be used as a reliable index of sedimentation under oxygenated bottom water conditions. However, this model does not appear to be strictly applicable to the formation of Ca-rhodochrosite in the anoxic deeps of the Baltic Sea. Jakobsen and Postma (1989) have shown that pore waters in the sediments from these deeps are greatly supersaturated with respect to both rhodochrosite and calcite. The dissolved Mn contents in the bottom waters of the deeps (> 12 mole/l) would not be high enough to facilitate deposition of Ca-rhodochrosite (Glasby et al., 1997). Both Huckriede and Meischner (1996) and Sternbeck and Sohlenius (1997) have therefore proposed that the formation of discrete horizons of Ca-rhodochrosite within the sediments of the Baltic deeps is related to periods of stagnation of the deeps. During periodic ushing of the deeps by well-oxygenated North Sea water, oxidation of Mn2+ in the bottom waters takes place to produce particulate MnO2 . During the subsequent stagnation, manganese is again reduced and enriched in the near-bottom waters from which it is then precipitated as a layer of Ca-rhodochrosite in the sediments. These data indicate that Ca-rhodochrosite is formed in the Baltic Sea deeps only when stagnant conditions develop again following the intermediate deposition of particulate MnO2 at the sediment surface in these deeps. Manganese is known to be easily leached from sediments in the Baltic Sea under reducing

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conditions (Glasby et al., 1997). The ultimate source of the manganese in Baltic Sea ferromanganese ores is believed to be glacial till (Zhamoida et al., 1996). Several authors have concluded that the formation of authigenic MnCO3 deposits is driven by microbial methanogenesis within the sediment column (Hein et al., 1987; Matsumoto, 1987; Curtis, 1995). According to the equations presented by Curtis (1995), manganese and iron reduction resulting from methanogenesis in the presence of sulphate ions produces rhodochrosite and pyrite respectively. Only in the absence of sulphate ions is siderite (FeCO3 ) produced (Carman and Rahm, 1997). This explains why siderite is not often reported in marine deposits. Diagenetic processes play a key role in recycling Mn and Fe in marine sediments. Recent papers describing these processes in detail have been presented by Santschi et al. (1990), Schulz et al. (1994), Thamdrup et al. (1994), Dhahar and Burdige (1996), Soetaert et al. (1996), Van Cappellen and Wang (1996), Haese et al. (1997) and Luther et al. (1998). For Co, there has been considerable speculation on its mode of uptake in deepsea manganese nodules and crusts as a consequence of its tendency to be associated with either Mn or Fe oxyhydroxides (Dillard et al., 1982, 1984; Halbach et al.1982; Crowther et al., 1984; Hem et al., 1985; Giovanoli and Arrhenius, 1988). According to Giovanoli and Arrhenius (1988), Co may subsitute as exchangeable Co2+ in marine manganates and then be oxidized to Co3+ by Mn4+ . Co3+ may also substitute for Fe3+ in Fe oxyhydroxide minerals in the nodules. Crowther et al. (1983), on the other hand, demonstrated that Co is incorporated in synthetic birnessite as Co(II) to pH 7 and as Co(III) above pH 8. Based on synthetic experiments, Hem et al. (1985) proposed that CoOOH is the principal solid phase in deep-sea manganese nodules. The fact that CoFe2 O4 and not CoOOH is the stable solid phase of Co under seawater conditions complicates this picture somewhat. For Ni, the occurrence of NiCO0 as the principal aquatic species in seawater 3 would have implications for the sorption of Ni on deep-sea manganese nodules since it is normally assumed that sorption of Ni2+ takes place on the surface of the nodules (Glasby and Thijssen, 1982). For Cu, the boundary between Cu2+ and CuCl2 as the dominant species in 3 seawater lies slightly above the normal range of redox conditions in seawater (EH of +0.48 V). At an EH of +0.48 V, the concentration of Cu2+ in seawater would still be sufcient for it to be incorporated into manganese nodules by sorption on the surface of negatively charged MnO2 (Glasby, 1974; Glasby and Thijssen, 1982). At somewhat lower EH values, however, the concentration of Cu2+ in seawater would decline drastically and the anionic species CuCl2 would be the dominant species. 3 Its sorption on MnO2 would be inhibited by charge considerations. This may well explain the high Ni/Cu ratios observed in cobalt-rich manganese crusts (max. 15) formed adjacent to the oxygen minimum zone where less oxidizing conditions prevail (Halbach et al., 1983, 1989; Dymond et al., 1984; Aplin and Cronan, 1985; Mangini et al., 1987; Meylan et al., 1990). Varentsov et al. (1985) has pointed out the role of hydrostatic pressure in controling the uptake of metal ions in manganese

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nodules from the World Ocean but our study would suggest that other factors are more important in the case of Cu. Interestingly, other authors have not considered the possibility of CuCl2 being a predominant species in seawater (Bruland, 1983; 3 Varentsov et al., 1985; Zaitseva and Varentsov, 1990). For As, it is generally assumed that sorption of an anionic As species, probably arsenate or HAsO2 , on ferric oxyhydroxide takes place in the marine environment 4 (Kunzendorf and Glasby, 1992; Metz and Trefry, 1993; Fuller et al., 1993; Rudnicki and Eldereld, 1993; Lilley et al., 1995; Widerlund and Ingri, 1995). In particular, Pokrovski et al. (1996) have suggested that H3 AsO0 may be the dominant arsenic 3 species in hydrothermal uids in the pH range 0-8 at temperatures of 20300 C (cf. Tossell, 1997). Our data indicate the presence of HAsO2 in seawater which 4 would explain the sorption of arsenic on ferric oxyhydroxides (cf. Vink, 1997). Nonetheless, the occurrence of Ba3 (AsO4 )2 as the stable solid phase at the pH of seawater does suggest that this mineral could occur in submarine hydrothermal deposits. This may explain the association of Ba and As in submarine hydrothermal iron-rich crusts (e.g., Binns et al., 1993; Stoffers et al., 1993). The above discussion is based on the assumption that the distribution and speciation of elements in the oceans is controlled by thermodynamic factors. As is well known, however, sorption reactions dominate in the marine environment (Turekian, 1977) with sorption of trace elements on Mn (Balistrieri and Murray, 1986) and Fe (Tessier et al., 1985; Liang and Morgan, 1990) oxyhydroxides being of particular importance. As an example, the association of elements with the Mn and Fe oxyhydroxide phases in marine manganese deposits is directly related to the element speciation in seawater and the physico-chemical properties of the carrier phase (Koschinsky and Halbach, 1995). The adsorption of Co, Ni and Cu on Mn oxyhydroxides and of Co and As on Fe oxyhydroxides should therefore be borne in mind.

5. Conclusions This study has shown that EH , pH diagrams calculated using the PHREEQC method are useful tools in determining the speciation of trace elements in seawater. These diagrams have the potential to establish the speciation of other elements in seawater. We believe that this approach can offer valuable insights into the marine geochemistry of these elements. However, it is necessary to calculate EH , pH diagrams for each specic situation if meaningful results are to be obtained.

Acknowledgements We would like to thank Martin Klling for helpful discussions. We thank John W. Morse for the editorial handling of the manuscript and an anonymous reviewer for helpful and constructive comments on the rst draft of this manuscript. This

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research was funded by the Deutsche Forschungsgemeinschaft (contribution no. 268 of Special Research Project SFB 261 at the University of Bremen).

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