Skip to main content
SpringerLink
Log in

Analytical and thermodynamic approaches to the mineralogical and compositional studies on anoxic sediments

  • Research Article
  • Published:
Journal of Soils and Sediments Aims and scope Submit manuscript

Abstract

Background, Aim and Scope

The identification of certain minerals directly in the raw sediment has proved to be difficult, if not impossible, because of their instability and/or low contents. This explains why the characterization/composition/crystalline nature of multiple (co)precipitates and solid solutions often necessitate the combined use of density separation methods and macro and microanalytical techniques, and in some cases the possible existence of certain mineral solids is only sustained from thermodynamic considerations. In this context, the comparison of porewater concentration profiles with thermodynamic calculations recently proved to be a convenient way of obtaining clues relative to the potential occurrence of natural minerals.

Methods

Porewaters and sedimentary-solid phases were extracted from sliced sediment samples collected in the Seine estuary (northern France), and studied as a function of sediment depth. Porewater concentration profiles were determined for Ca, Fe, Mg, Mn, Na, P and Sr using inductively coupled plasma atomic emission spectroscopy, and for dissolved sulfur using square wave, cathodic stripping voltammetry. To obtain information about sediment mineralogy, sedimentary solid phases were analysed directly and after density separation with a heavy liquid (CHBr3) by means of several techniques: X-ray diffraction; electron spin resonance and micro-Raman spectroscopies. Furthermore, using sequential extraction procedures, the chemical speciation versus depth of several elements (Al, Ca, Fe, Mg, Mn, P, Pb, Sr, Ti, and Zn) and particularly sulfur [i.e. acid volatile sulfides (AVS) and chromium reducible sulfurs (CRS)] were undertaken.

Results and Discussion.

From these analytical data, some thermodynamic calculations [using ion activity products (LAP)] were attempted for the anoxic porewaters where most of the ionic complexing species were measured to support the involvement of relevant geochemical equilibria between these ions and some metals and the existence of any discrete solid phases (calcite, dolomite, greigite and probably vivianite, apatite and siderite), as well as coprecipitates and solid solutions in calcium carbonate.

Conclusions

Thermodynamic equilibria in sedimentary media are rarely achieved because many chemical processes in these systems are established in long periods. Nevertheless, these calculations remain useful to increase our insight into the considered system. They help to support our view about the possible existence of certain minerals (iron sulfides, calcite, dolomite...). They also help account for the real power of ESR for indicating the presence of hypothesised solid solutions, MnxCa1-xC03. The critical investigations of the authors, however, reveal some weaknesses of XRD and Raman microscopy for identifying minor minerals/precipitates, which result from combinations between the inorganic anions P04 3-, C03 2- and S2- and the metallic cations Fe2+, Mn2+, Mg2+, and Sr2+.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. AFNOR a. n., (1990): in Eaux Méthodes ďEssais (AFNOR ed.), Paris, 191–194

  2. Batina N, Ciglenecki I, and Cosovic B (1992): Determination of elemental sulphur, sulfide and their mixtures in electrolyte solutions by a.c. voltametry. Anal Chim Acta 267, 157–164

    Article  CAS  Google Scholar 

  3. Batley GE (1990): Trace Element Speciation: Analytical Methods and Problems, CRC Press, Inc., Boca Raton, Florida, 350 pp

    Google Scholar 

  4. Berner RA (1970): Sedimentary pyrite formation. Amer J Sci 268,1–23

    CAS  Google Scholar 

  5. Bertolin A, Mazzocchin GA, Rudello D, Ugo P (1997): Seasonal and depth variability of reduced sulfur species and metal ions in mudflat pore-waters of the Venice lagoon. Mar Chem 59,127–140

    Article  CAS  Google Scholar 

  6. Billon G, Ouddane B, Boughriet A(2001): Artefacts in the speciation of sulfides in anoxic sediments. The Analyst 126, 1805–1809

    Article  CAS  Google Scholar 

  7. Billon G, Ouddane B, Boughriet A (2001): Chemical speciation of sulfur compounds in surface sediments from three bays (Fresnaye, Seine and Authie) in northern France, and identification of some factors controlling their generation. Talanta 53, 971–981

    Article  CAS  Google Scholar 

  8. Billon G, Ouddane B, Laureyns J, Boughriet A (2001): Chemistry of metal sulfides in anoxic sediments. PCCP 3, 3586–3592

    CAS  Google Scholar 

  9. Boesen C, Postma D (1988): Pyrite formation in anoxic environments of the Baltic. Am J Sci 288, 575–603

    CAS  Google Scholar 

  10. Boughriet A, Laureyns J (1998): Laser confocal micro-Raman spectroscopic study of anoxic estuarine sediments. Europ Micr and Anal 53, 5–7

    Google Scholar 

  11. Boughriet A, De-Figueiredo RS, Laureyns J, Recourt P (1997): Identification of newly generated iron phases in recent anoxic sediments: 57Fe Mössbauer and micro Raman spectroscopic studies. J Chem Soc Faraday Trans 93, 3209–3215

    Article  CAS  Google Scholar 

  12. Boughriet A, Ouddane B, Wartel M (1992): Electron spin resonance investigations of Mn compounds and free radicals in particles from the Seine river and its estuary. Mar Chem 37,149–169

    Article  CAS  Google Scholar 

  13. Boughriet A, Ouddane B, Cordier C, Laureyns J (1998): Thermodynamic, spectroscopic and magnetic studies on anoxic sediments from the Seine river estuary. J Chem Soc, Faraday Trans 94, 3677–3683

    Article  CAS  Google Scholar 

  14. Busenberg E, Plummer LN, Parker VB (1984): The solubility of strontianite (SrC03) in C02-H20 solution between 2 and 91ÐC, the association constants of SrHC03+ (aq) and SrC03 between 5 and 80ÐC, and an evaluation of the thermodynamic properties of Sr2+ and SrC03(aq) at 25ÐC and 1 atm total pressure. Geochim Cosmochim Acta 48, 2021–2035

    Article  CAS  Google Scholar 

  15. Canfield DE, Raiswell R, Westrich JT, Reaves CM, Berner RA (1986): The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales. Chem Geol 54, 149–155

    Article  CAS  Google Scholar 

  16. Chester R (1990): Marine Geochemistry. Academic Division of Unwin Hyman Ltd, London, 698 pp

    Google Scholar 

  17. Coleman ML, Hedrick DB, Lovley DR, White DC, Pye K, (1993): Reduction of Fe(III) in sediment by sulphate-reducing bacteria. Nature 361, 436–438

    Article  CAS  Google Scholar 

  18. Cornwell JC and Morse JW (1987): The characterization of iron sulfide minerals in anoxic marine sediments. Mar Chem 22, 193–206

    Article  CAS  Google Scholar 

  19. Davison W (1991): The solubility of iron sulphides in synthetic and natural waters at ambient temperature. Aquat Sci 53, 309–329

    Article  Google Scholar 

  20. Davison W, Buffle J, Devitre R (1988): Direct polarographic determination of 02, Fe(II), Mn(II), S(-II) and related species in anoxic waters. Pure & Appl Chem 60 (10) 1535–1548

    Article  CAS  Google Scholar 

  21. Ehrlich HL (1990): Geomicrobiology, 2ed Marcel Dekker Press, New York, 393 pp

    Google Scholar 

  22. Gagnon C, Mucci A, Pelletier E (1995): Anomalous accumulation of acid-volatil sulphides (AVS) in coastal marine sediments, Saguenay Fjord, Canada. Geochim Cosmochim Acta 59, 2663–2675

    Article  CAS  Google Scholar 

  23. Golterman HL, Meyer ML (1985): The geochemistry of two hard water rivers, the Rhine and the Rhone. Part 4. The apparent solubility product of hydroxy-apatite. Hydrobio 126, 25–30

    Article  CAS  Google Scholar 

  24. Golterman HL (1995): The role of the iron-hydroxide-phos- phate-sulfide system in the phosphate exchange between sediments and overlying water. Hydrobio 297, 43–54

    Article  CAS  Google Scholar 

  25. Holtzapffel T (1985): Les Minéraux Argileux: Préparation, Analyse Diffractométrique et Détermination, publication NÐ12, Société Géologique du Nord (France), 136 pp

    Google Scholar 

  26. Howarth RW, Stewart JWB, Ivanov MV (1992): Sulfur Cycling on the continents: Wetlands, Terrestrial Ecosystems and Associated Water Bodies, John Wiley & Sons, Chichester, 350 pp

    Google Scholar 

  27. Huerta-Diaz MA, Morse JW (1992): Pyritisation of trace metals in anoxic marine sediments. Geochim Cosmochim Acta 56, 2681–2702

    Article  CAS  Google Scholar 

  28. Huerta-Diaz MA, Tessier A, Carignan R (1998): Geochemistry of trace metals associated with reduced sulfur in freshwater sediments. Appl Geochem 13, 213–233

    Article  CAS  Google Scholar 

  29. Johnson KS (1982): Solubility of rhodochrosite (MnC03) in water and seawater. Geochim and Cosmochim Acta 46, 1805–1809

    Article  CAS  Google Scholar 

  30. Kittrich JA and Peryea FJ (1986): Determination of the Gibbs free energy of formation of magnesite by solubility methods. Soil Sci Soc Am J 50, 243–245

    Article  Google Scholar 

  31. Lasorsa B, Casas A (1996): A comparison of sampling and analytical methods for determination of acid volatile sulfides in sediments. Mar Chem 52, 211–220

    Article  CAS  Google Scholar 

  32. Martin JM, Nirel P, Thomas AJ (1987): Sequential extraction techniques: promises and problems. Mar Chem 22, 313–341

    Article  CAS  Google Scholar 

  33. Morel FMM (1983): Principles of Aquatic Chemistry, John Wiley & Sons, New York, 446 pp

    Google Scholar 

  34. Mucci A (1990): Chemistry of low-temperature abiotic calcites: experimental studies on coprecipitation, stability, and fractionation. Aqua Sci 3, 217–254

    CAS  Google Scholar 

  35. Nassrallah-Aboukaïs N, Boughriet A, Fisher JC, Wartel M, Langelin HR, Aboukaïs A (1996): Electron paramagnetic resonance (ESR) study of Cu2+ and Mn2+ ions interacting as probes with calcium carbonate during the transformation of vaterite into cubic calcite. J Chem Soc, Faraday Trans 92, 3211–3216

    Article  Google Scholar 

  36. Nassrallah-Aboukaïs N, Boughriet A, Gengembre L, Aboukaïs A (1998): Manganese(II)/vaterite/water systems: spectroscopic and thermodynamic study. J Chem Soc, Faraday Trans 94, 2399–2405

    Article  Google Scholar 

  37. Plummer LN, Busenberg E (1982): The solubilities of calcite, aragonite and vaterite in C02-H20 solutions between 0 and 90ÐC and an evaluation of the aqueous model for the system CaC03-C02-H20. Geochim Cosmochim Acta 46, 1011–1040

    Article  CAS  Google Scholar 

  38. Raiswell R, Berner RA (1985): Pyrite formation in euxinic and semi-euxinic sediments. Amer J Sci 285, 710–724

    CAS  Google Scholar 

  39. Rozan TF, Benoit G, Luther-III GW (1999): Measuring metal sulfide complexes in oxic river waters with square wave voltammetry. Environ Sci Technol 33, 3021–3026

    Article  CAS  Google Scholar 

  40. Schecher WD and McAvoy DC (1998): MINEQL+: A Chemical Equilibrium Modeling System; version 4 for Windows. Environmental Research Software, 318 pp

  41. Simpson SL, Apte S, Batley GE (1998): Effect of short-term resuspension events on the oxidation of cadmium, lead, and zinc sulfide phases in anoxic estuarine sediments. Environ Sci Technol 32, 620–625

    Article  CAS  Google Scholar 

  42. Smith RM and Martell AE (1976): Critical Stability Constants. Plenum Press, New York, 257 pp

    Google Scholar 

  43. Stumm W and Morgan JJ (1981): Aquatic Chemistry, 2rd edition, Wiley-Interscience Publication, New York, 780 pp

    Google Scholar 

  44. Stumm W (1992): Chemistry of the Solid-Water Interface: Processes at the Mineral-Water and Particle-Water Interface in Natural Systems. Wiley-Interscience Publication, New York, 428 pp

    Google Scholar 

  45. Tessier A, Campbell PGC (1988): in Metal Speciation: Theory, Analysis and Application (Kramer JR, Allen HE, eds), Lewis, Chelsea, 183–194

  46. Tessier A, Campbell PGC, Bisson M (1979): Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry 51, 844–851

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. ELICO (UMR CNRS 8013), Laboratoire de Chimie Analytique et Marine Université des Sciences et Technologies de Lille 1, Bât C8 (2ème étage), F-59655, Villeneuve ďAscq Cedex, France

    Gabriel Billon & Baghdad Ouddane

  2. Laboratoire de Spectrochimie Infrarouge et Raman CNRS: Centre ďes et de Recherches Lasers et Applications, Universitèdes Sciences et Technologies de Lille, F-9655, Villeneuve ďAscq Cedex, France

    Jacky Laureyns

  3. Universitè ďArtois, LU.T. de Béthune Département de Chimie, Rue de >Universit<, B.R 819, F-62408, Béthune Cedex, France

    Abdel Boughriet

Authors
  1. Gabriel Billon
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Baghdad Ouddane
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jacky Laureyns
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Abdel Boughriet
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Baghdad Ouddane.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Billon, G., Ouddane, B., Laureyns, J. et al. Analytical and thermodynamic approaches to the mineralogical and compositional studies on anoxic sediments. J Soils & Sediments 3, 180–187 (2003). https://doi.org/10.1065/jss2003.04.074

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1065/jss2003.04.074

Keywords

Search

Navigation