Geothermal systems can provide significant amounts of hydrothermal sulfur to surface waters, increasing salinity and avoiding some of the common anthropic uses. The objective of this study was to investigate the sedimentary neoformation of S-bearing phases in organic matter-rich sediments from a saline lake with hydrothermal inputs (Sochagota Lake, Colombia). Detrital kaolinite and quartz are the main minerals of the materials deposited in the Sochagota Lake. Neoformed clay minerals (illite and illite-dioctahedral vermiculite mixed layers) are concentrated in the central and northern part of the lake in sediments with high organic matter content. The most organic matter-rich materials are characterized by S-bearing minerals: mackinawite, pyrite, and elemental sulfur (S°). FESEM, high-resolution transmission electron microscopy (HRTEM), EDS, and Raman microspectrometry have revealed the presence of cell-shape aggregates of mackinawite nanoparticles filling the inner part of plant fragments, indicating that microorganisms were involved in the hydrothermal sulfur uptake. The alteration of mackinawite in free sulfide excess environment produced the formation of framboidal pyrite. The evolution to conditions with the presence of oxygen favored the formation of complex S° morphologies.
Electron microscopy and sediment geochemical data from a river basin (the upper Chicamocha river basin, UCRB, Boyacá province, Colombia) affected by anthropogenic activities (wastewater discharges, smelting and agricultural activities) showed the existence of heterogeneously distributed Zn particles in the sediments and sediments with Zn contents above the regional background (42 mg/kg). The objective of this study was to evidence the ZnS sedimentary neoformation in organic matter rich sediments deposited in anthropogenic reservoirs to reveal the processes involved in the sedimentary uptake of Zn from potential pollution sources. The highest Zn concentrations are found in clay minerals and organic matter-rich sediments (up to 427 mg/kg) deposited in slow-flowing reaches of the river associated to La Playa dam. Quartz-rich sediments poor in organic matter deposited in fast flowing segments of the river show very low Zn contents (1–12 mg/kg). Electron microscopy images showed ZnS nanoparticles forming cell-shaped aggregates suggesting that sulfate-reducing microorganisms acted as templates for the partial binding of Zn and for the nucleation and growth of zinc sulfide minerals. A good correlation of Zn with total organic carbon (r = 0.936) and the low potential redox of these sediments (−233 mV) suggest that organic matter was able to maintain oxygen depleted conditions appropriate to the Zn accumulation in the sediments. Our results demonstrate that potentially toxic Zn, originating from anthropic activities, was partially immobilized in organic matter-rich sediments through the precipitation of sulfides.
In this investigation, we showed that high salinity promoted by hydrothermal inputs, reducing conditions of sediments with high content in organic matter, and the occurrence of an appropriate clay mineral precursor provide a suitable framework for low-temperature illitization processes. We studied the sedimentary illitization process that occurs in carbonaceous sediments from a lake with saline waters (Sochagota Lake, Colombia) located at a tropical latitude. Water isotopic composition suggests that high salinity was produced by hydrothermal contribution. Materials accumulated in the Sochagota Lake’s southern entrance are organic matter-poor sediments that contain detrital kaolinite and quartz. On the other hand, materials formed at the central segment and near the lake exit (north portion) are enriched in organic matter and characterized by the crystallization of Fe-sulfides. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), and energy dispersive X-ray spectrometry (EDX) data allowed for the identification of illite and illite-dioctahedral vermiculite mixed layers (I-DV), which are absent in the southern sediments. High humidity and temperate climate caused the formation of small-sized metastable intermediates of I-DV particles by the weathering of the source rocks in the Sochagota Lake Basin. These particles were deposited in the low-energy lake environments (middle and north part). The interaction of these sediments enriched in organic matter with the saline waters of the lake enriched in hydrothermal K caused a reducing environment that favored Fe mobilization processes and its incorporation to I-DV mixed layers that acted as mineral precursor for fast low temperature illitization, revealing that in geothermal areas clays in lakes favor a hydrothermal K uptake.
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