Spectroscopic investigations and density functional theory calculations reveal differences in retention mechanisms of lead and copper on chemically-modified phytolith-rich biochars.

A better understanding of different retention mechanisms of potentially toxic elements (PTEs) by biochars during the remediation of contaminated sites is critically needed. In this study, different spectroscopic techniques including synchrotron-based micro-X-ray fluorescence (µ-XRF), X-ray absorption fine structure (XAFS), and near-edge XAFS spectroscopy (NEXAFS), were used to investigate the spatial distributions and retention mechanisms of lead (Pb) and copper (Cu) on phytolith-rich coconut-fiber biochar (CFB), and ammonia, nitric acid and hydrogen peroxide modified CFB (MCFB) (i.e., ACFB, NCFB and HCFB). The µ-XRF analyses indicated that sorption sites on ACFB and NCFB were more efficient compared to those on CFB and HCFB to bind Pb/Cu. XAFS analyses revealed that the percentage of Pb species as Pb(C2H3O2)2 increased from 22.2% (Pb-loaded CFBs) to 47.4% and 41.9% on Pb-loaded NCFBs and HCFBs, while the percentage of Cu(OH)2 and Cu(C2H3O2)2 increased from 5.8% to 32.8% (Cu-loaded CFBs) to 41.5% and 43.4% (Cu-loaded NCFBs), and 27.1% and 35.1% (Cu-loaded HCFBs), respectively. Due to their similar atomic structures of Pb/Cu, Pb(C2H3O2)2/Pb-loaded montmorillonite and Cu(C2H3O2)2/Cu(OH)2 were identified as the predominant Pb/Cu species observed in Pb- and Cu-loaded MCFBs. The NEXAFS analyses of carbon confirmed that increasing amounts of carboxylic groups were formed on HCFB and NCFB by oxidizing carbon-containing functional groups, which could provide additional active binding sites for Pb/Cu retention. Results from the X-ray photoelectron spectroscopy analyses of nitrogen showed that azido-groups of ACFB played major roles in Pb/Cu retention, while amide-groups and pyridine-groups of NCFB primarily participated in Pb/Cu retention. Overall, density functional theory calculations suggested that silicate and the synergistic effect of hydroxyl and carboxylic-groups on MCFBs were highly efficient in Pb retention, while azido-groups and/or carboxylic-groups played major roles in Cu retention. These results provide novel insights into the PTE retention mechanisms of MCFBs.

Lead and copper-induced hormetic effect and toxicity mechanisms in lettuce (Lactuca sativa L.) grown in a contaminated soil.

Lead (Pb) and copper (Cu) contamination seriously threatens agricultural production and food safety. This study aims to investigate Pb and Cu induced hormetic effect and toxicity mechanisms in lettuce (Lactuca sativa L.) and establish reliable empirical models of potentially toxic elements (PTEs) transfer in the soil-plant system. The content and distribution of Pb and Cu at subcellular levels in lettuce plants were examined using inductively coupled plasma-mass spectrometry, differential centrifugation and micro-X-ray fluorescence spectroscopy. The PTE-loaded capacity of Pb that ensures food safety was lower than that of Cu in the studied soil, but the PTE-loaded capacity of Pb that limits yield was higher than that of Cu. Lead in lettuce roots mainly accumulated in the cell wall (41%), while Cu mainly accumulated in the vacuoles (46%). The Pb and Cu were primarily distributed in the radicle of lettuce seeds under severe PTE stress, resulting in no seed development. Iron plaque formed on the root surface of lettuce seedlings and sequestered Pb and Cu via chelation. At the same concentration, lettuce was less tolerant to Cu in contaminated soil than Pb due to the higher activity of Cu ions in the soil. Lead was more phytotoxic to lettuce than Cu, however, since the radicle emerged from the seed under severe Cu levels, while it did not protrude under severe Pb levels. The potentially damaging effect of Pb in the visually healthy lettuce appeared to be higher than that of Cu under the same soil contamination level.

Synchrotron radiation based STXM analysis and micro-XRF mapping of differential expression of extracellular thiol groups by Acidithiobacillus ferrooxidans grown on Fe(2+) and S(0).

The differential expression of extracellular thiol groups by Acidithiobacillus ferrooxidans grown on substrates Fe(2+) and S(0) was investigated by using synchrotron radiation based scanning transmission X-ray microscopy (STXM) imaging and microbeam X-ray fluorescence (µ-XRF) mapping. The extracellular thiol groups (SH) were first alkylated by iodoacetic acid forming Protein-SCH2COOH and then the P-SCH2COOH was marked by calcium ions forming P-SCH2COOCa. The STXM imaging and µ-XRF mapping of SH were based on analysis of SCH2COO-bonded Ca(2+). The results indicated that the thiol group content of A. ferrooxidans grown on S(0) is 3.88 times to that on Fe(2+). Combined with selective labeling of SH by Ca(2+), the STXM imaging and µ-XRF mapping provided an in situ and rapid analysis of differential expression of extracellular thiol groups.

Thermophilic archaeal community succession and function change associated with the leaching rate in bioleaching of chalcopyrite.

The community succession and function change of thermophilic archaea Acidianus brierleyi, Metallosphaera sedula, Acidianus manzaensis and Sulfolobus metallicus were studied by denaturing gradient gel electrophoresis (DGGE) analysis of amplifying 16S rRNA genes fragments and real-time qPCR analysis of amplifying sulfur-oxidizing soxB gene associated with chalcopyrite bioleaching rate at different temperatures and initial pH values. The analysis results of the community succession indicated that temperature and initial pH value had a significant effect on the consortium, and S. metallicus was most sensitive to the environmental change, A. brierleyi showed the best adaptability and sulfur oxidation ability and predominated in various leaching systems. Meanwhile, the leaching rate of chalcopyrite closely related to the consortium function embodied by soxB gene, which could prove a desirable way for revealing microbial sulfur oxidation difference and tracking the function change of the consortium, and for optimizing the leaching parameters and improving the recovery of valuable metals.

Sulfur oxidation activities of pure and mixed thermophiles and sulfur speciation in bioleaching of chalcopyrite.

The sulfur oxidation activities of four pure thermophilic archaea Acidianus brierleyi (JCM 8954), Metallosphaera sedula (YN 23), Acidianus manzaensis (YN 25) and Sulfolobus metallicus (YN 24) and their mixture in bioleaching chalcopyrite were compared. Meanwhile, the relevant surface sulfur speciation of chalcopyrite leached with the mixed thermophilic archaea was investigated. The results showed that the mixed culture, with contributing significantly to the raising of leaching rate and accelerating the formation of leaching products, may have a higher sulfur oxidation activity than the pure cultures, and jarosite was the main passivation component hindering the dissolution of chalcopyrite, while elemental sulfur seemed to have no influence on the dissolution of chalcopyrite. In addition, the present results supported the former speculation, i.e., covellite might be converted from chalcocite during the leaching experiments, and the elemental sulfur may partially be the derivation of covellite and chalcocite.

Investigation of elemental sulfur speciation transformation mediated by Acidithiobacillus ferrooxidans.

The speciation transformation of elemental sulfur mediated by the leaching bacterium Acidithiobacillus ferrooxidans was investigated using an integrated approach including scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, energy dispersive X-ray spectroscopy, and X-ray absorption near edge spectroscopy (XANES). Our results showed that when grown on elemental sulfur powder, At. ferrooxidans ATCC23270 cells were first attached to sulfur particles and modified the surface sulfur with some amphiphilic compounds. In addition, part of the elemental sulfur powder might be converted to polysulfides. Furthermore, sulfur globules were accumulated inside the cells. XANES spectra of these cells suggested that these globules consisted of elemental sulfur bound to thiol groups of protein.