| Abstract |
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.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 (CHBr$_{3}$) 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.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.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, Mn$_{x}$Ca$_{1-x}$C0$_{3}$. 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 P0$_{4}$ $^{3-}$, C0$_{3}$ $^{2-}$ and S$^{2-}$ and the metallic cations Fe$^{2+}$, Mn$^{2+}$, Mg$^{2+}$, and Sr$^{2+}$. |
