Abstract
The reactions of many trace metals in natural waters are affected by their speciation or form. This will affect the biological uptake (Anderson and Morel 1982) and toxicity (Sunda and Ferguson 1983) as well as the solubility (Liu and Millero 1999). For example, Fe(II) and Mn(II) are biologically available for marine organisms, while Fe(III) and Mn(IV) are not normally available. Although the form of an element in natural waters can be four phases (solid, gas, colloid and dissolved), we will only consider the form of a metal in the dissolved state. The definition of a dissolved metal is defined by the filter size used to separate solid and colloidal phases from the soluble form. In the past, this separation was made with a 0.45 μm filter, and in more recent work smaller size filters are used (~o.2 μm). The speciation of metals is controlled by ionic interactions of the metals with inorganic (Cl-, OH-, CO 2-3 , etc.) and organic (fulvic and humic acids) ligands. The dissolved forms of a metal like Fe in sea water can include:
-
Free ions: Fe2+, Fe3+
-
Inorganically Complexed: Fe(OH)+, Fe(OH)2, FeCO3 and Fe(CO3) 2-2 , FeCl2+, FeCl +2 , FeSO +4 , Fe(SO4) 2-2 , Fe(OH)2+, Fe(OH)3, FeCO +3 , and Fe(CO3) 2-2
-
Organically Complexed: FeL, where L can be a wrde range or unKrnown nlatural llgands (fulvic and humic acids, siderifores, etc.)
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Anderson MA, Morel FM (1982) The influence of aqueous iron chemistry on the uptake of iron by the coastal diatom Thalassiosira weissflogii. Limnol Oceanogr 27:789–813
Baes CF, Mesmer RE (1976) The hydrolysis of cations. John Wiley and Sons, New York
Berg CMG van den (1982) Determination of copper complexation with natural organic ligands in seawater by equilibration with Mn02. II. Experimental procedures and application to surface seawater. Mar Chem 11:323–342
Baes CF, Mesmer RE (1976) The hydrolysis of cations. John Wiley and Sons, New York
Berg CMG van den (1982) Determination of copper complexation with natural organic ligands in seawater by equilibration with Mn02. II. Experimental procedures and application to surface seawater. Mar Chem 11:323–342
Berg CMG van den (1995) Evidence for organic complexation of iron in seawater. Mar Chem 50:139–157
Breeman N van (1973) Calculation of activity coefficients in natural waters. Geochim Cosmochim Acta 37:101–107
Bruland KW (1989) Complexation of zinc by natural organic ligands in the central North Pacific. Limnol Oceanogr 34:269–285
Bruland KW (1992) Complexation of cadmium by natural organic ligands in the central North Pacific. Limnol Oceanogr 37:1008–1017
Byrne RH Jr, Kester DR (1974) Inorganic speciation of boron in seawater. J Mar Res 32:119–127
Byrne RH, Kester DR (1976) Solubility of hydrous ferric oxide and iron speciation in seawater. Mar Chem 4:255–274
Byrne RH, Luo Y-R (2000) Direct observations of nonintegral hydrous ferric oxide solubility products: K*so =[Fe3+] [H1–2.86. Geochim Cosmochim Acta 64:1873–1877
Campbell DM, Millero FJ, Roy R, Roy L, Lawson M, Vogel KM, Moore CP (1993) The standard potential for the hydrogen — silver, silver chloride electrode in synthetic seawater. Mar Chem 44:221–233
Clegg SL, Whitfield M (1991) Activity coefficients in natural waters. In: Pitzer KS (ed) Activity coefficients in electrolyte solutions. CRS, Boca Raton, FL, pp 279–434
Clegg SL, Whitfield M (1995) A chemical model of seawater including dissolved ammonia and the stoichiometric dissociation constant of ammonia in estuarine water and seawater from -2 to 40 °C. Geochim Cosmochim Acta 59:2403–2421
Coale KH, Bruland KW (1988) Copper complexation in the Northeast Pacific. Limnol Oceanogr 33:1084–1101
Criss C, Millero FJ (1996) Modeling the heat capacities of aqueous 1-i electrolyte solutions with Pitzer’s equations. J Phys Chem 91:1288–1294
Criss C, Millero FJ (1999) Modeling the heat capacities of high valence-type electrolyte solutions with Pitzer’s equations. J Solution Chem 28:849–864
Culberson C, Pytkowicz RM (1973) Ionization of water in seawater. Mar Chem 1:309–316
Culberson C, Pytkowicz RM, Hawley JE (1970) Seawater alkalinity determination by the pH method. J Mar Res 28:15–21
Culberson C, Latham G, Bates RG (1978) Solubilities and activity coefficients of calcium and strontium sulfates in synthetic seawater at o.5 and 25 °C. J Phys Chem 82:2693–2699
Dickson AG (1990a) Thermodynamics of the dissociation of boric acid in synthetic seawater from 273.15 to 318.15 K. Deep-Sea Res 37:755–766
Dickson AG(1990b) Standard potential of the reaction: AgCl(s) + 1/2H2(g) = Ag(s) + HCl(aq), and the standard acidity constant of the HSO4 in synthetic sea water from 273.15 to 318.15 K. J Chem Thermodyn 22:113–127
Dickson AG, Riley JP (1979a) The estimation of acid dissociation constants in seawater from potentiometric titrations with strong base. I. The ion product of water — Kw. Mar Chem 7:89–99
Dickson AG, Riley JP (1979b) The estimation of acid dissociation constants in seawater from potentiometric titrations with strong base. II. The dissociation of phosphoric acid. Mar Chem 7:101–109
Dickson AG, Whitfield M (1981) An ion-association model for estimating acidity constants (at 251 C and 1 atm total pressure) in electrolyte mixtures related to seawater (ionic strength < i mol kg H20). Mar Chem 10:315–333
Felmy AR, Weare JH (1986) The prediction of borate mineral equilibria in natural waters: Application to Searles Lake, California. Geochim Cosmochim Acta 50:2771–2783
Garrels RM, Thompson ME (1962) A chemical model for seawater at 25 °C and one atmosphere total pressure. Am J Sci 260:57–66
Gieskes JMT (1966) The activity coefficients of sodium chloride in mixed electrolyte solutions at 25 °C. Physik Chemie Neue Folge 50:78–90
Gledhill M, Berg CMG van den (1994) Determination of complexation of iron(III) with natural organic complexing ligands in seawater using cathodic stripping voltammetry. Mar Chem 47:41–54
Goyet C, Poisson A (1989) New determination of carbonic acid dissociation constants in seawater as a function of temperature and salinity. Deep-Sea Res 36:1635–1654
Greenberg JP, Møller N (1989) The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-K-Ca-Cl-S04-H20 system to high concentration from o to 25o °C. Geochim Cosmochim Acta 53:2503–2518
Hansson I (1972) An analytical approach to the carbonate system in seawater. PhD dissertation, University of Göteborg, Sweden Hansson I (1973) A new set of acidity constants for carbonic acid and boric acid in seawater. Deep-Sea Res 20:461–478
Harvie CE, Weare JH (1980) The prediction of mineral solubilities in natural waters: The Na-K-Mg-CaSO4-Cl-H20 system from zero to high concentration at 25 °C. Geochim Cosmochim Acta 44:981–997
Harvie CE, Møller N, Weare JH (1984) The prediction of mineral solubilities in natural waters: The NaK-Mg-Ca-H-Cl-SO4-OH-HCO3–0O3–0O3-H2O system to high ionic strengths at 25 °C. Geochim Cosmochim Acta 48:723–752
He S, Morse JW (1993) The carbonic acid system and calcite solubility in aqueous Na-K-Ca-Mg-Cl-SO4 solutions from o to 90 °C. Geochim Cosmochim Acta 57:3533–3554
Hering JG, Sunda WG, Ferguson RL, Morel FMM (1987) A field comparison of two methods for the determination of copper complexation: Bacterial bioassay and fixed-potential amperometry. Mar Chem 20:299–312
Johansson O, Wedborg M (1980) The ammonia-ammonium equilibrium in seawater at temperatures between 5 and 25 °C. j Solution Chem 9:37–44
Johnson KE, Pytkowicz RM (1981) The activity of NaCl in seawater of 10–40%o salinity and 5–25 °C at 1 atmosphere. Mar Chem 10:85–91
Kester DR, Pytkowicz RM (1967) Determination of the apparent dissociation constants of phosphoric acid in seawater. Limnol Oceanogr 12:243–252
Khoo KH, Ramette RW, Culberson CH, Bates RG (1977a) Determination of hydrogen ion concentrations in seawater from 5 to 4o °C: standard potentials at salinities from 20 to 45%o. Anal Chem 49:29–34.
Khoo KH, Culberson CH, Bates RG (1977b) Thermodynamics of ammonium ion in seawater from 5 to 40 °C. J Solution Chem 6:281–290
Kramer CJM, Duinker JC (1984) Complexation capacity and conditional stability constants for copper of sea and estuarine waters, sediment extracts and colloids. In: Kramer CJM, Duinker JC (eds) Complexation of trace metals in natural waters. Nijhoff/Junk, The Hague, The Netherlands, pp 217–228
Kuma K, Nishioka J, Matsunaga K (1996) Controls on iron(III) hydroxide solubility in seawater: The influence of pH and natural organic chelators. Limnol Oceanogr 41:396
Liu SX, Millero FJ (1999)The solubility of iron in sodium chloride solutions. Geochim Cosmochim Acta 63:3487–3497
Liu SX, Millero FJ (2002) The solubility of iron in seawater. Mar Chem 17:43–54
Mantoura RFC, Dickson A, Riley JP (1978) The complexation of metals with humic materials in natural waters. Est Coastal Mar Sci 6:387–408
Mehrbach C, Culberson CH, Hawley JE, Pytkowicz RM (1973) Measurement of the apparent dissociation constants of carbonic acid in seawater at atmospheric pressure. Limnol Oceanogr 18:897–907
Millero FJ (1979a) Effects of pressure and temperature on activity coefficients. In: Pytkowicz RM (ed) Activity coefficients in electrolyte solutions, vol II. CRC Press, Boca Raton, FL, pp 63–151
Millero FJ (1979b) The thermodynamics of the carbonate system in seawater. Geochim Cosmochim Acta 43:1651–1661
Millero FJ (1982) Use of models to determine ionic interactions in the natural waters. Thalassia Jugoslavica 1–4:253–291
Millero FJ (1986) The pH of estuarine waters. Limnol Oceanogr 31(4):839–847
Millero FJ (1990a) Effect of speciation on the rates of oxidation of mnetals. In: Melchior D, Bassett R (eds) Chemical modeling in aqueous systems II. ACS Books, Washington D.C., pp 447–460
Millero FJ (1990b) Marine solution chemistry and ionic interactions. Mar Chem 30:205–229
Millero FJ (1992) Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim Cosmochim Acta 56:3123–3132
Millero FJ (1995) Thermodynamics of carbon dioxide system in the oceans. Geochim Cosmochim Acta 59:661–677
Millero FJ (1998) Solubility of Fe(III) in seawater. Earth Planet Sci Lett 154:323–330
Millero FJ (1996) Chemical oceanography. CRC Press, Boca Raton, FL
Millero FJ (2001) The physical chemistry of natural waters. Wiley Scientific, N.Y.
Millero FJ, Hawke DJ (1992) Ionic interactions of divalent metals in natural waters. Mar Chem 40:19–48
Millero FJ, Pierrot D (1998) A chemical model for natural waters. Aquatic Geochem 4:153–199
Millero FJ, Roy R(1997) A chemical model for the carbonate system in natural waters. Croatia Chemica Acta 70:1–38
Millero FJ, Schreiber DR (1982) Use of the ion pairing model to estimate activity coefficients of the ionic components of natural waters. Am J Sci 282:1508–1540
Millero FJ, Plese T, Fernandez M (1988) The dissociation of hydrogen sulfide in seawater. Limnol Oceanogr 33:269–274
Millero FJ, Sharma VK, Karn B (1991) The rate of reduction of Cu(II) with hydrogen peroxide in seawater. Mar Chem 36:71–83
Millero FJ, Johnson R, Vega C, Sharma VK, Sotolongo S (1992) The effect of ionic interactions on the rates of reduction of Cu(II) with H202 in aqueous solutions. J Solution Chem 21:1271–1287
Millero FJ, Yao W, Aicher J(1995) The speciation of Fe(II) and Fe(III) in natural waters. Mar Chem 50:21–39
Moffett JW, Zika RG (1987) Solvent extraction of copper acetylacetonate in studies of copper (II) speciation in seawater. Mar Chem 21:301–313
Møller N (1988) The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-Ca-Cl-S04-H20 system, to high temperature and concentration. Geochim Cosmochim Acta 52:821–837
Mucci A (1983) The solubility of calcite and aragonite in seawater at various salinities, temperatures and one atmosphere total pressure. Am J Sci 283:780–799
Pabalan RT, Pitzer KS (1987) Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperature for mixtures in the system Na-K-Mg-C1-S04-OH-H20. Geochim Cosmochim Acta 51:2429–2443
Pitzer KS (1975) Thermodynamics of electrolytes. V. Effects of higher order electrostatic terms. J Solution Chem 3:249–265
Pitzer KS (1979) Theory: Ion interaction approach. In: Pytkowicz RM (ed) Activity coefficients in electrolyte solutions, vol I. CRC Press, Boca Raton, FL, pp 157–208
Pitzer KS (1991) Theory: Ion interaction approach: Theory and data collection. In: Pitzer KS (ed) Activity coefficients in electrolyte solutions, 2nd edn, vol I. CRC Press, Boca Raton, FL, pp 75–153
Pitzer KS, Kim JJ (1974) Thermodynamics of electrolytes. IV. Activity and osmotic coefficients for mixed electrolytes. J Am Chem Soc 96:5701–5707
Pitzer KS, Mayorga G (1973) Thermodynamics of electrolytes. II. Activity and osmotic coefficients for strong electrolytes with one or both ions univalent. J Phys Chem 77:2300–2308
Pitzer KS, Mayorga G (1974) Thermodynamics of electrolytes. III. Activity and osmotic coefficients for 2–2 electrolytes. J Solution Chem 3:539–546
Platford RF (1965) The activity coefficient of sodium chloride in seawater. J Mar Res 23:55–62
Platford RF, Dafoe T (1965) The activity coefficient of sodium sulfate in seawater. J Mar Res 23:63–68
Roy RN, Roy LN, Lawson M, Vogel KM, Porter-Moore C, Davis W, Millero FJ, Campbell DM (1993) The dissociation constants of carbonic acid in seawater at salinities 5 to 45 and temperatures o to 45 °C. Mar Chem 44:249–259
Rue EL, Bruland KW (1995) Complexation of iron(III) by natural organic ligands in the central North Pacific as determined by competitive equilibration/adsorptive cathodic stripping voltammetric method. Mar Chem 50:117–138
Sharma VK, Millero FJ (1988) Oxidation of Copper(I) in seawater. Environ Sci Technol 22:768–771
Sharma VK, Millero FJ (1989) The oxidation of Cu(I) with H202 in natural waters. Geochim Cosmochim Acta 53:2269–2276
Silvester LF, Pitzer KS (1978) Thermodynamic of electrolytes. X. Enthalpy and the effect of temperature on the activity coefficients. J Solution Chem 7:327–337
Simonson JM, Roy RN, Gibbons JJ (1987a) Thermodynamics of aqueous mixed potassium carbonate, bicarbonate, and chloride solutions to 368 K. J Chem Eng Data 32:41–45
Simonson JM, Roy RN, Connole J, Roy LN, Johnson DA (1987b) The thermodynamics of aqueous borate solutions. II. Mixtures of boric acid with calcium or magnesium borate and chloride. J Solution Chem 16:791–803
Simonson JM, Roy RN, Mrad D, Lord P, Roy LN, Johnson DA, (1988) The thermodynamics of aqueous borate solutions, I. Mixtures of boric acid with sodium or potassium borate and chloride. J Solution Chem 17:435–446
Sohn ML, Hughes MC (1981) Metal complex formation constants of some sedimentary humic acids with Zn(II), Cu(II) and Cd(II). Geochim Cosmochim Acta 45:2393–2399
Spencer RJ, Møller N,Weare JH (1990) The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-K-Ca-Mg-Cl-SO4-H20 system at temperatures below 25 °C. Geochim Cosmochim Acta 54:575–590
Stumm W, Morgan JJ (1996) Aquatic chemistry: Chemical equilibria and rates in natural waters, 3rd edn. Wiley-Interscience, New York
Sunda WG, Ferguson RL (1983) Sensitivity of natural bacterial communities to additions of copper and to cupric ion activity: A bioassay of copper complexation in seawater. In: Wong CS, Boyle E, Bruland KW, Burton JD, Goldberg ED (eds) Trace metals in seawater. Plenum Press, New York, pp 871–891
Sunda WG, Hanson AK (1987) Measurement of free cupric ion concentration in seawater by a ligand competition technique involving copper sorption onto C18 SEP-PAK cartridges. Limnol Oceanogr 32:537–551
Sunda WG, Klaveness D, Palumbo AV (1984) Bioassays of cupric ion activity and copper complexation. In: Kramer CJM, Duinker JC(eds) Complexation of trace metals in natural waters. Nijhoff/Junk, The Hague, The Netherlands, pp 399–409
Thompson ME (1966) Magnesium in sea water: An electrode measurement. Science 153:866–867
Truesdale AH, Jones BF (1969) Ion association of natural brines. Chem Geol 4:1–62
Turner DR, Whitfield M, Dickson AG (1981) The equilibrium speciation of dissolved components in freshwater and seawater at 25 °C and i atm pressure. Geochim Cosmochim Acta 45:855–881
Vazquez F, Zhang JZ, Millero FJ (1989) Effect of trace metals on the oxidation rates of H2S in seawater. Geophys Res Lett 16:1363–1366
Whitfield M (1975) The extension of chemical models for seawater to include trace components. Geochim Cosmochim Acta 39:1545–1557
Wu J, Luther GW (1995) Complexation of Fe(III) by natural organic ligands in the Northwest Atlantic Ocean by a competitive ligand equilibration method and kinetic approach. Mar Chem 50:159–177
Yao W, Millero FJ (1995) The chemistry of the anoxic waters in the Framvaren Fjord, Norway. Aquatic Chem 1:53–88
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2002 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Millero, F., Pierrot, D. (2002). Speciation of Metals in Natural Waters. In: Gianguzza, A., Pelizzetti, E., Sammartano, S. (eds) Chemistry of Marine Water and Sediments. Environmental Science. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-04935-8_8
Download citation
DOI: https://doi.org/10.1007/978-3-662-04935-8_8
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-07559-9
Online ISBN: 978-3-662-04935-8
eBook Packages: Springer Book Archive