Abstract
In the summer of 1993, a number of chemical parameters (H2S, O2, pH, TA, TCO2, NH +4 , PO 3−4 , SiO2, Mn2+ and Fe2+) were measured in the Framvaren Fjord, a permanently super-anoxic fjord in southern Norway. The extremely steep gradient of sulfide near the interface suggests that other than downward flux of oxygen, three other possible oxidants, particulate manganese and iron oxides, phototrophic sulfur oxidation bacteria and horizontally transported oxygen account for the oxidation of the upward flux of H2S. Water intrusion through the sill accounts for the temperature inflection above the interface, which, together with internal waves (Stigerbrandt and Molvaer, 1988), may cause fluctuations of the depth of interface. Significant gradients of hydrographic properties and chemical species between 80–100 m suggest that there is a “second interface” at about 90 m that separates the deep and older bottom waters. A stoichiometric model is applied to examine the biogeochemical cycles of S, C, N and P in the Framvaren. High C:S, C:N and C:P ratios are found while the nutrients (N, P) have Redfield ratio. Based on the C:N:P ratio of 155:16:1 in organic matter, about 30% of sulfide produced by sulfate reduction is estimated to be removed by processes such as oxidation, formation of FeS2, degassing and incorporation into organic matter. The rates of oxidation of H2S by Mn and Fe oxides in the water near the interface were slightly faster than the observed values in the laboratory, probably due to the presence of bacteria.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Aizenshtat, Z., Stoler, A., and Nielsen, H., (1983) The geochemical sulfur enrichment of recent organic matter by polysulfides in the solar-lake. InAdvances in Organic Geochemistry 1981 (ed. M. Bjoroy), Wiley, Chichester, pp. 279–288.
Anderson, L. G., Dyrssen, D., and Hall, P. O. J. (1988) On the sulfur chemistry of a super-anoxic fjord, Framvaren, South Norway.Mar. Chem. 23, 283–293.
Anderson, L. G., Dyrssen, D., and Skei, J. (1987) Formation of chemogenic calcite in super-anoxic seawater — Framvaren southern Norway.Mar. Chem. 20, 361–176.
Bates, R. G. and Acree, S. F. (1943) pH values of certain phosphate chloride mixtures and the second dissociation constant of phosphoric acid from 0°C to 60°C.J. Res. Natl. Bur. Stand. 30, 129–155.
Bates, R. G. and Pinching, G. D. (1949) Acidic dissociation constant of ammonium ion at 0 to 50°C, and the base strength of ammonia.J. Res. Natl. Bur. Stand. 42, 419–430.
Breland, J. N. and Byrne, R. H. (1993) Spectrophotometric determination of the total alkalinity of sea water using bromocresol green.Deep-Sea Res. 40, 629–641.
Brewer, P. G. and Spencer, D. W. (1971) Colorimetric determination of manganese in anoxic waters.Limnol. Oceanogr. 16, 107–110.
Brewer, P. G. and Murray, J. M. (1973) Carbon, nitrogen and phosphorus in the Black Sea.Deep-Sea Res. 20, 803–818.
Burdige, D. J. and Nealson, K. H. (1986) Chemical and microbiological studies of sulfide-mediated manganese reduction.Geomicrobiol. J. 4, 361–387.
Busey, R. H. and Mesmer, R. E. (1977) Ionization equilibria of silicic acid and polysilicate formation in aqueous sodium chloride solutions to 300°C.Inorg. Chem. 1, 2444–2450.
Carpenter, J. H. (1965) The Chesapeake Bay Institute Technique for the Winkler dissolved oxygen method.Limnol. Oceanogr. 10, 141–143.
Chen, K. Y. and Morris, J. C. (1972) Kinetics of oxidation of aqueous sulfide by O2.Environ. Sci. Technol. 6, 529–537.
Cline, I. D. (1969) Spectrophotometric determination of hydrogen sulfide in nature waters.Limnol. Oceanogr. 14, 454–458.
Craig, H., Broecker, W. S., and Spencer, D. (1981)GEOSECS Pacific Expedition, Sections and Profiles. U.S. Government Printing Office, Washington, D.C., Vol. 251.
Crosby, S. A., Glasson, D. R., Cuttler, A. H., Butler, I., Turner, D. R., Whitfield, M., and Millward, S. E. (1983) Surface areas and porosities of Fe(III) and Fe(II)-derived oxyhydroxides.Environ. Sci. Technol. 17, 709–713.
Culberson, C. and Pytkowicz, R. M. (1973) Ionization of water in seawater.Mar. Chem. 1, 309–316.
Dickson, A. G. and Riley, J. P. (1979a) The estimation of acid dissociation constants in seawater media from potentiometric titrations with strong base. I. The ionic product of water —Kw.Mar. Chem. 7, 89–99.
Dickson, A. G. and Riley, J. P. (1979b) The estimation of acid dissociation constants in seawater media from potentiometric titrations with strong base. II. The dissociation of phosphoric acid.Mar. Chem. 7, 101–109.
Dickson, A. G. (1981) An exact definition of total alkalinity and a procedure for the estimation of alkalinity and total CO2 from titration data.Deep-Sea Res. 28, 609–623.
Dickson, A. G. (1990) Thermodynamics of the dissociation of boric acid in synthetic seawater from 273.15 to 318.15 K.Deep-Sea Res. 37, 755–766.
Dickson, A. G. (1993) pH buffers for sea water media based on the total hydrogen ion concentration scales.Deep-Sea Res. 40, 107–118.
Dyrssen, D., Hall, P., Haraldsson, C., Iverfeldt, A., and Westerlund, S. (1984) Trace metal concentrations in the anoxic bottom water of Framvaren. InComplexation of Trace Metals in Natural Waters (eds. C. J. M. Kramer and J. C. Duinker), Martinus Nijhoff/Dr W. Junk Publisher, The Hague/Boston/Lancaster, pp. 239–245.
Dyrssen, D. (1985) Some calculations on Black Sea chemical data.Chem. Scr. 5, 199–205.
Dyrssen, D. (11986) Stagnant sulphidic basin waters.Sc. Total Env. 58, 161–173.
Dyrssen, D. (1987)A Man-Made Sulfide Producer. ACS National Meeting. Vol. 27, No. 2. Division of Environmental Chemistry, American Chemical Society, Washington, pp. 93–95.
Dyrssen, D. (1989) Biogenic sulfur in two different marine environments.Mar. Chem. 28, 241–249.
Friederich, G. E., Codispoti, L. A., and Sakamoto, C. M. (1990) Bottle and pumpcast data from the 1988 Black Sea expedition. Technical Report No. 90–3. Monterey Bay Aquarium Research Institute.
Goyet, C., Bradshaw, A. L., and Brewer, P. G. (1991) The carbonate system in the Black Sea.Deep-Sea Res. 38, (Suppl.): S1049-S1068.
Grasshoff, K. (1975) The hydrochemistry of landlocked basins and fjords. InChemical Oceanography (eds. J. P. Riley and G. Skirrow), Vol. 2, Academic Press, London, pp. 611–645.
Hansson, I. (1973) A new set of acidity constants for carbonic acid and boric acid in seawater.Deep-Sea Res. 20, 461–478.
Haraldsson, C. and Westerlund, S. (1988) Trace metals in the water columns of the Black Sea and Framvaren Fjord.Mar. Chem. 23, 417–424.
Hecky, R. E., Campbell, P., and Hendzel, L. L. (1993) The stoichiometry of carbon, nitrogen, and phosphorus in particulate matter of lakes and oceans.Limnol. Oceanogr. 38, 709–724.
Ingri, N. (1959) Equilibrium studies of polyanions. IV. Silicate ions in NaCl medium.Acta Chem. Scand. 13, 758–770.
Jacobs, L., Emerson S., and Skei, J. (1985) Partitioning and transport of metals across the O2/H2S interface in a permanently anoxic basin: Framvaren Fjord, Norway.Geochim. Cosmochim. Acta 49, 1433–1444.
Jannasch, H. W. (1991) Microbial processes in the Black Sea water column and top sediment: An overview. InBlack Sea Oceanography (eds. E. Izdar and J. W. Murray), Kluwer, Dordrecht, pp. 271–286.
Johansson, O. and Wedborg, M. (1979) Stability constants of phosphoric acid in seawater of 5–40‰ salinity and temperatures of 5–25°C.Mar. Chem. 8, 57–69.
Johansson, O. and Wedborg, M. (1980) The ammonia-ammonium equilibrium in sea-water at temperatures between 5°C and 25°C.J. Sol. Chem. 9, 37–44.
Johnson, K. M., King, A. E., and McN. Sieburth, J. (1985) Coulometric TCO2 analyses for marine studies: an introduction.Mar. Chem. 16, 61–82.
Jørgensen, B. B., Fossing, H., Wirsen, C. O., and Jannasch, H. W. (1991) Sulfide oxidation in the anoxic Black Sea chemocline.Deep-Sea Res. 38, (Suppl.), S1083-S1103.
Kemp, S. (1990) Alkalinity: The link between anaerobic basins and shallow water carbonates?Naturwissenschaffer 7, 426–427.
Khoo, K. H., Culberson, C. H., and Bates, R. G. (1977) Thermodynamics of ammonium ion in seawater from 5 to 40°C.J. Sol. Chem. 6, 281–290.
Krein, E. B. and Aizenshtat, Z. (1994) The formation of isoprenoid sulfur compounds during diagenesis: Simulated sulfur incorporation and thermal transformation.Org. Geochem. 21, 1015–1025.
Krom, M. D. and Berner, R. A. (1981) The diagenesis of phosphorus in a near shore marine sediment.Geochim. Cosmochim. Acta 4, 207–216.
Landing, W. M. and Westerlund, S. (1988) The solution chemistry of iron (II) in Framvaren Fjord.Mar. Chem. 23, 329–343.
Little, K. (1971) Practical analysis of high purity chemicals — V. Precision silver chloride gravimetry.Talanta 18, 927–933.
Luther III, G. W., Church, T. M., and Powell, D. (1991) Sulfur speciation and sulfide oxidation in the water column of the Black Sea.Deep-Sea Res. 38 (Suppl.), S1121–1137.
Martens, C. S. (1993) Recycling efficiencies of organic carbon, nitrogen, phosphorus and reduced sulfur in rapidly depositing coastal sediments. InInteractions of C, N, P and S Biogeochemical Cycles and Global Change (eds. R. Wollast, F. T. Mackenzie, and L. Chou), Springer-Verlag, Berlin, Heidelberg, pp. 379–400.
Mckee, B. A. (1993) Biogeochemical Investigations of Framvaren Fjord. Preliminary Data Report June 4–9 1993, Louisiana Universities Marine Center.
Mckee, B. A. and Todd, J. F. (1993) Uranium behavior in a permanently anoxic fjord: Microbial control?Limnol. Oceanogr. 38, 408–414.
Millero, F. J. (1979) The thermodynamics of the carbonic acid system in seawater.Geochim. Cosmochim. Acta 43, 1651–1661.
Millero, F. J., Plese, T., and Fernandez, M. (1988) The dissociation of hydrogen sulfide in sea-water.Limnol. Oceanogr. 33, 269–274.
Millero, F. J. (1991) The oxidation of H2S in Framvaren Fjord.Limnol. Oceanogr. 36, 1007–1014.
Millero, F. J., Zhang, J.-Z., Fiol, S., Sototlongo, S., Roy, R., Lee, K., and Mane, S. (1993a) The use of buffers to measure the pH of seawater.Mar. Chem. 44, 143–152.
Millero, F. J., Zhang, J.-Z., Lee, K., and Campbell, D. M. (1993b) Titration alkalinity of seawater.Mar. Chem. 44, 153–165.
Mopper, K. and Kieber, D. J. (1991) Distribution and biological turnover of dissolved organic compounds in the water column of the Black Sea.Deep-Sea Res. 38 (Suppl.), S1021–1047.
Mucci, A. (1983) The solubility of calcite and aragonite in seawater at various salinities, temperatures and one atmosphere total pressure.Amer. J. Sci. 283, 780–799.
Murray, J. M. (1974) The surface chemistry of hydrous manganese dioxide.J. Colloid. Interface Sci. 46, 357–371.
Murray, J. M. and Izdar, E. (1989) The 1988 Black Sea oceanography expedition: Overview and new discoveries.Oceanography 2, 15–21.
Murray, J. M., Top, Z., and Ozsoy, E. (1991) Hydrographic properties and ventilation of the Black Sea.Deep-Sea Res. 38, (Suppl.), S663-S689.
Murray, J. M., Codispoti, L. A., and Friederich, G. E. (1994) Redox environments: The suboxic zone in the Black Sea. InAquatic Chemistry (eds. C. P. Huang, C. R. O'Melia, and J. J. Morgan), American Chemistry Society, pp. 000–000.
Naes, K., Skei, J. M., and Wassmann, P. (1988) Total particulate and organic fluxes in anoxic Framvaren waters.Mar. Chem. 23, 257–268.
Parsons, T. R., Maita, Y., Lalli, C. M. (1984)A Manual of Chemical and Biological Methods for Sea-Water Analysis. Pergamon Press, Oxford.
Peng, T.-H. and Broecker, W. S. (1987) C/P ratios in marine detritus.Global Biogeochem. Cycles 1, 155–161.
Redfield, A. C., Ketchum, B. H., and Richards, F. A. (1963) The influence of organisms on the composition of seawater. InThe Sea, Vol. 2 (ed. M. N. Hill), Interscience, New York, pp. 26–77.
Richards, F. A. (1965) Anoxic basins and fjords. In:Chemical Oceanography, Vol. 1, (ed. J. P. Riley and G. Skirrow), Academic Press, New York, pp. 611–645.
Roy, R. N., Roy, L. N., Vogel, K. M., Porter-Moore, C., Pearson, T., Good, C. E., Millero, F. J., and Campbell, D. M. (1993) The dissociation constants of carbonic acid in seawater in salinities 5 to 45 and temperature 0 to 45°C.Mar. Chem. 44, 249–267.
Schwertmann, U. and Cornell, R. M. (1991)Iron Oxides in the Laboratory. Weinhein, New York.
Shaffer, G. (1986) Phosphate pumps and shuttles in the Black Sea.Nature 321, 515–517.
Skei, J. M. (1983) Geochemical and sedimentological consideration of a permanent anoxic fjord — Framvaren, South Norway.Sediment Geol. 36, 132–145.
Skei, J. M. (1986) The biogeochemistry of Framvaren. A permanent Anoxic Fjord Near Farsund, South Norway. Data Report 1931–1985, Norwegian Institute for Water Research.
Skei, J. M. (1988a) Framvaren — Environmental setting.Mar. Chem. 23, 209–218.
Skei, J. M. (1988b) Formation of framboidal iron sulfide in the water of a permanently anoxic fjord — Framvaren, south Norway.Mar. Chem. 23, 345–352.
Smethie Jr., W. M. (1987) Nutrient regeneration and denitrification in low oxygen fjords.Deep-Sea Res. 34, 983–1006.
Sørensen, K. (1988) The distribution and biomass of phytoplankton and phototrophic bacteria in Framvaren, a permanently anoxic fjord in Norway.Mar. Chem. 23, 229–241.
Spencer, D., Broecker, W. S., Craig, H., and Weiss, R. F. (1982)GEOSECS Indian Ocean Expedition, Sections and Profiles. U.S. Government Printing Office, Washington, D.C. Vol. 2, 198 pp.
Stigebrandt, A. and Molvaer, J. (1988) On the water exchange of Framvaren.Mar. Chem. 23, 219–228.
Takahashi, T., Broecker, W., and Langer, S. (1985) Redfield ratio based on chemical data from isopycnal surfaces.J. Geophys. Res. 90, 6907–6924.
Tebo, B. M. and Nealson, K. H. (1984) Microbial mediation of Mn(II) and Co(II) precipitation at the O2/H2S interfaces in two anoxic fjords.Limnol. Oceanogr. 29, 1247–1258.
Vairavamurthy, A., Mopper, K., and Taylor, B. F. (1992) Occurrence of particle-bound polysulfides and significance of their reaction with organic matters in marine sediments.Geophys. Res. Lett. 19, 2043–2046.
Wetzel, R. G. (1975)Limnology. Saunders, Philadelphia.
Yao, W. and Millero, F. J. (1993) The rate of sulfide oxidation by δMnO2 in seawater.Geochim. Cosmochim. Acta 57, 3359–3365.
Yao, W. and Millero, F. J. (1994) Oxidation of hydrogen sulfide by Mn(IV) and Fe(III) (hydr)oxides in seawater. InGeochemical Transformation of Sedimentary Sulfur (eds. M. A. Vairavamurthy and M. A. A. Schoonen), ACS Press, Washington D.C., submitted.
Zhang, J.-Z. and Millero, F. J. (1993) The chemistry of the anoxic waters in the Cariaco Trench.Deep-Sea Res. 40, 1023–1041.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Yao, W., Millero, F.J. The chemistry of the anoxic waters in the Framvaren Fjord, Norway. Aquat Geochem 1, 53–88 (1995). https://doi.org/10.1007/BF01025231
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF01025231