Contrasted microbial community colonization of a bauxite residue deposit marked by a complex geochemical context.

Bauxite residue is the alkaline byproduct generated during alumina extraction and is commonly landfilled in open-air deposits. The growth in global alumina production have raised environmental concerns about these deposits since no large-scale reuses exist to date. Microbial-driven techniques including bioremediation and critical metal bio-recovery are now considered sustainable and cost-effective methods to revalorize bauxite residues. However, the establishment of microbial communities and their active role in these strategies are still poorly understood. We thus determined the geochemical composition of different bauxite residues produced in southern France and explored the development of bacterial and fungal communities using Illumina high-throughput sequencing. Physicochemical parameters were influenced differently by the deposit age and the bauxite origin. Taxonomical analysis revealed an early-stage microbial community dominated by haloalkaliphilic microorganisms and strongly influenced by chemical gradients. Microbial richness, diversity and network complexity increased significantly with the deposit age, reaching an equilibrium community composition similar to typical soils after decades of natural weathering. Our results suggested that salinity, pH, and toxic metals affected the bacterial community structure, while fungal community composition showed no clear correlations with chemical variations.

Differences in bulk and microscale yttrium speciation in coal combustion fly ash.

Coal combustion ash is a promising alternative source of rare earth elements (REE; herein defined as the 14 stable lanthanides, yttrium, and scandium). Efforts to extract REE from coal ash will depend heavily on the location and speciation of these elements in the ash. This study sought to identify the major chemical forms of yttrium (Y), as a representative REE in coal fly ash samples selected from major coal sources in the United States. Y speciation was evaluated using both bulk scale analyses (sequential extractions, Y K-edge X-ray absorption near-edge spectroscopy - XANES) and complementary analyses at the micron scale (micro-focus X-ray fluorescence and micro-XANES). Sequential selective extractions revealed that the REE were primarily in the residual (unextracted fraction) of coal fly ash samples. Extraction patterns for yttrium resembled those of the lanthanides, indicating that these elements were collectively dispersed throughout the aluminosilicate glass in fly ash. Bulk XANES analysis indicated that Y coordination states resembled a combination of Y-oxides, Y-carbonate, and Y-doped glass, regardless of ash origin. However, in the microprobe analysis, we observed "hotspots" of Y (∼10-50 µm) in some samples that included different Y forms (e.g., Y-phosphate) not observed in bulk measurements. Overall, this study demonstrated that yttrium (and potentially other REEs) are entrained in the glass phase of fly ash and that microscale investigations of individual high-REE regions in fly ash samples do not necessarily capture the dominant speciation.

Speciation of Mercury in Selected Areas of the Petroleum Value Chain.

Petroleum, natural gas, and natural gas condensate can contain low levels of mercury (Hg). The speciation of Hg can affect its behavior during processing, transport, and storage so efficient and safe management of Hg requires an understanding of its chemical form in oil, gas and byproducts. Here, X-ray absorption spectroscopy was used to determine the Hg speciation in samples of solid residues collected throughout the petroleum value chain including stabilized crude oil residues, sediments from separation tanks and condensate glycol dehydrators, distillation column pipe scale, and biosludge from wastewater treatment. In all samples except glycol dehydrators, metacinnabar (ß-HgS) was the primary form of Hg. Electron microscopy on particles from a crude sediment showed nanosized (<100 nm) particles forming larger aggregates, and confirmed the colocalization of Hg and sulfur. In sediments from glycol dehydrators, organic Hg(SR)2 accounted for ∼60% of the Hg, with ∼20% present as ß-HgS and/or Hg(SR)4 species. ß-HgS was the predominant Hg species in refinery biosludge and pipe scale samples. However, the balance of Hg species present in these samples depended on the nature of the crude oil being processed, i.e. sweet (low sulfur crudes) vs sour (higher sulfur crudes). This information on Hg speciation in the petroleum value chain will inform development of better engineering controls and management practices for Hg.

Fate of zinc oxide and silver nanoparticles in a pilot wastewater treatment plant and in processed biosolids.

Chemical transformations of silver nanoparticles (Ag NPs) and zinc oxide nanoparticles (ZnO NPs) during wastewater treatment and sludge treatment must be characterized to accurately assess the risks that these nanomaterials pose from land application of biosolids. Here, X-ray absorption spectroscopy (XAS) and supporting characterization methods are used to determine the chemical speciation of Ag and Zn in sludge from a pilot wastewater treatment plant (WWTP) that had received PVP coated 50 nm Ag NPs and 30 nm ZnO NPs, dissolved metal ions, or no added metal. The effects of composting and lime and heat treatment on metal speciation in the resulting biosolids were also examined. All added Ag was converted to Ag2S, regardless of the form of Ag added (NP vs ionic). Zn was transformed to three Zn-containing species, ZnS, Zn3(PO4)2, and Zn associated Fe oxy/hydroxides, also regardless of the form of Zn added. Zn speciation was the same in the unamended control sludge. Ag2S persisted in all sludge treatments. Zn3(PO4)2 persisted in sludge and biosolids, but the ratio of ZnS and Zn associated with Fe oxy/hydroxide depended on the redox state and water content of the biosolids. Limited differences in Zn and Ag speciation among NP-dosed, ion-dosed, and control biosolids indicate that these nanoparticles are transformed to similar chemical forms as bulk metals already entering the WWTP.

Integrated approaches of x-ray absorption spectroscopic and electron microscopic techniques on zinc speciation and characterization in a final sewage sludge product.

Integration of complementary techniques can be powerful for the investigation of metal speciation and characterization in complex and heterogeneous environmental samples, such as sewage sludge products. In the present study, we combined analytical transmission electron microscopy (TEM)-based techniques with X-ray absorption spectroscopy (XAS) to identify and characterize nanocrystalline zinc sulfide (ZnS), considered to be the dominant Zn-containing phase in the final stage of sewage sludge material of a full-scale municipal wastewater treatment plant. We also developed sample preparation procedures to preserve the organic and sulfur-rich nature of sewage sludge matrices for microscopic and spectroscopic analyses. Analytical TEM results indicate individual ZnS nanocrystals to be in the size range of 2.5 to 7.5 nm in diameter, forming aggregates of a few hundred nanometers. Observed lattice spacings match sphalerite. The ratio of S to Zn for the ZnS nanocrystals is estimated to be 1.4, suggesting that S is present in excess. The XAS results on the Zn speciation in the bulk sludge material also support the TEM observation that approximately 80% of the total Zn has the local structure of a 3-nm ZnS nanoparticle reference material. Because sewage sludge is frequently used as a soil amendment on agricultural lands, future studies that investigate the oxidative dissolution rate of ZnS nanoparticles as a function of size and aggregation state and the change of Zn speciation during post sludge-processing and soil residency are warranted to help determine the bioavailability of sludge-born Zn in the soil environment.

Competitive sorption of Pb(II) and Zn(II) on polyacrylic acid-coated hydrated aluminum-oxide surfaces.

Natural organic matter (NOM) often forms coatings on minerals. Such coatings are expected to affect metal-ion sorption due to abundant sorption sites in NOM and potential modifications to mineral surfaces, but such effects are poorly understood in complex multicomponent systems. Using poly(acrylic acid) (PAA), a simplified analog of NOM containing only carboxylic groups, Pb(II) and Zn(II) partitioning between PAA coatings and α-Al2O3 (1-102) and (0001) surfaces was investigated using long-period X-ray standing wave-florescence yield spectroscopy. In the single-metal-ion systems, PAA was the dominant sink for Pb(II) and Zn(II) for α-Al2O3(1-102) (63% and 69%, respectively, at 0.5 µM metal ions and pH 6.0). In equi-molar mixed-Pb(II)-Zn(II) systems, partitioning of both ions onto α-Al2O3(1-102) decreased compared with the single-metal-ion systems; however, Zn(II) decreased Pb(II) sorption to a greater extent than vice versa, suggesting that Zn(II) outcompeted Pb(II) for α-Al2O3(1-102) sorption sites. In contrast, >99% of both metal ions sorbed to PAA when equi-molar Pb(II) and Zn(II) were added simultaneously to PAA/α-Al2O3(0001). PAA outcompeted both α-Al2O3 surfaces for metal sorption but did not alter their intrinsic order of reactivity. This study suggests that single-metal-ion sorption results cannot be used to predict multimetal-ion sorption at NOM/metal-oxide interfaces when NOM is dominated by carboxylic groups.