RESUMO
Illite-rich sediments from the Laguna Honda wetland, an eutrophicated hypersaline wetland with waters enriched in Mg and Ca surrounded by olive groves in the Guadalquivir Basin River (South Spain), are polluted by elevated concentrations of gold (up to 21.9 ppm) due to agricultural practices. The highest gold contents appear in the shore sediments of the lake, where up to 20 µm homoaggregates of fused gold nanoparticles (AuNp) are found. Small nanoaggregates of up to six fused gold nanoparticles and very few isolated nanoparticles around 1 nm in size can also be observed to form heteroaggregates of AuNp-mica, especially in the deeper sediments in the central part of the wetland, where Au concentrations are lower (up to 1.89 ppm). The high nanoparticle concentration caused by the inappropriate application of pesticides favors nanoparticle collision in the wetland's Mg- and Ca-rich waters and the fast coagulation and deposition of Au homoaggregates in the gold-rich shore sediment of the lake. The interaction of gold nanoparticles with the abundant illite particles in the wetland's hypersaline waters promotes the simultaneous formation of low-density Au-illite heteroaggregates, which are transported and deposited in the less-rich-in-gold sediments of the central part of the lake. The small sizes of the isolated AuNp and AuNp-fused contacts of the aggregates suggest modifications in the original nanoparticles involving dissolution processes. The presence of bacterial communities resistant to heavy metal stress (Luteolibacter and Maricaulis), as well as the activity of sulfate-reducing bacteria (SRB) and particularly sulfur-oxidizing bacteria (SOB) communities from the shore sediments, favored the high-Eh and low-pH conditions adequate for the destabilization and transport of AuNp.
RESUMO
This research investigates the influence of water composition, the presence of seasonal algal mats, detrital inputs and the activity of microorganisms on the crystallization of aragonite in the sediments deposited in the hypersaline Laguna Honda wetland (S of Spain). The high alkaline and hypersaline waters (pH > 9.2 and C.E. > 70 mS/cm) of the wetland lake are rich in SO42- (>24,000 mg/l), Cl- (>21,000 mg/l), Na+ (>11,000 mg/l) Mg2+ (>8400 mg/l) and Ca2+ (>1000 mg/l), and are supersaturated for dolomite, calcite and aragonite. Sediments have lower pH values than column waters, oscillating from 8.54 in the low Eh (up to -80.9 mV) central deep sediments and 6.33 in the shallower higher Eh (around -13.6 mV) shore sediments. Erosion of the surrounding olive groves soils produced detrital silicates rich sediments with concretions of carbonate or sulfate. Aragonite (up to 19 %) and pyrite (up to 13 %) are mainly concentrated in the organic matter rich samples from the upper part of the sediment cores, whereas gypsum is preferably concentrated in low organic matter content samples. Mineral crusts containing a MgAl silicate phase, epsomite, halite and gypsum are precipitated on the floating algal mats covering the wetland waters. Floating algal mats deposit increased the organic matter content of the upper sediments which promoted the presence of fermentative microorganisms, sulfate-reducing bacteria (SRB) and sulfur-oxidizing bacteria (SOB) communities and variations of Eh that influence the authigenesis of carbonate and S-bearing minerals. Replacement of poorly crystalline MgSi phases infilling algal cells by aragonite was favored in the organic matter rich sediments with low Eh values and important SRB communities that promoted sulfate bioreduction processes to form pyrite. Aragonite precipitation was favored by the increase of carbonate and bicarbonate concentration produced by the SRB oxidation of organic matter, the CO2 degassing by high summer temperatures and the CO2 uptake by photosynthesis of the algal mats.