Clinoptilolite and iron sorption/desorption under multiple pH conditions: Testing a substrate for passive treatment of acidic, iron-rich solutions.

Equilibrium sorption and desorption experiments were conducted with clinoptilolite to evaluate the potential sorption/desorption of iron during different pH conditions. Sorption experiments indicated a partitioning of 0% to 17% of the iron in solution given pH of 2 to 4. The pH 2 solution was able to desorb 70% of the iron that was captured from a pH 3 solution. The largest desorption and sorption of iron and corresponding pH represent the end points of iron capture primarily by sorption/exchange. These endpoints are the estimated pHpzc of 2.5 and the initial precipitation point of iron(II) at pH ~3.5. This acidity range is where clinoptilolite is able to capture iron without precipitation or the occurrence of full surface protonation. The inability of the highest acidity to remove all sorbed iron represents the greater bound iron that will not readily desorb with a change in pH. This retained iron creates a metastable state of the clinoptilolite that has a lower sorption capacity but reflects the ability of clinoptilolite to retain a sorbed transition metal with changes in pH. As pH varies, clinoptilolite may evolve in a sequence of metastable states reflective of its ability to capture or retain metals. PRACTITIONER POINTS: Clinoptilolite is a capable reactive substrate, but its sorption/exchange effectiveness at low and variable pH and ability to retain captured metals was unknown. Clinoptilolite retains its metal capture properties to a pH of 2.5 where surface protonation and mineral degradation likely occurs. The ability of clinoptilolite to retain captured iron under greater acidity reflects an evolution of its sorption/retention capacity.

Dielectrophoretic ultra-high-frequency characterization and in silico sorting on uptake of rare earth elements by Cupriavidus necator.

Rare earth elements (REEs) are widely used across different industries due to their exceptional magnetic and electrical properties. In this work, Cupriavidus necator is characterized using dielectrophoretic ultra-high-frequency measurements, typically in MHz range to quantify the properties of cytoplasm in C. necator for its metal uptake/bioaccumulation capacity. Cupriavidus necator, a Gram-negative bacteria strain is exposed to REEs like europium, samarium, and neodymium in this study. Dielectrophoretic crossover frequency experiments were performed on the native C. necator species pre- and post-exposure to the REEs at MHz frequency range. The net conductivity of native C. necator, Cupriavidus europium, Cupriavidus samarium, and Cupriavidus neodymium are 15.95 ± 0.029 µS/cm, 16.15 ± 0.028 µS/cm, 16.05 ± 0.029 µS/cm, 15.61 ± 0.005 µS/cm respectively. The estimated properties of the membrane published by our group are used to develop a microfluidic sorter by modeling and simulation to separate REE absorbed C. necator from the unabsorbed native C. necator species using COMSOL Multiphysics commercial software package v5.5.

Application of dielectrophoresis towards characterization of rare earth elements biosorption by Cupriavidus necator.

This work presents the dielectric characterization of rare earth elements (REEs) biosorption by Cupriavidus necator using dielectrophoretic crossover frequency measurements. Traditional means of characterizing biomass for biosorption is limited and time consuming. In this research we are presenting, for the first time, an electrokinetic method termed as dielectrophoresis (DEP) for the characterization of biosorption (uptake) of rare earth elements (REEs) by gram negative bacteria - Cupriavidus necator. To characterize, a 3mm-diameter point and planar microwell device platform is used to measure the DEP crossover frequency that yields the dielectric properties of the targeted biosorbents. Quantified dielectric properties of native Cupriavidus necator (REE-) and those exposed to rare earth elements (REE+): europium, neodymium, and samarium revealed a substantial change in the surface characteristics of the Cupriavidus necator after exposure to the REE solution. The response of C. necator to changes in REE exposure is substantially different for europium but similar between neodymium and samarium. Statistically both the REE+ and REE- groups dielectric signatures were significantly different proving that the REEs were absorbed by the bacteria. This research will revolutionize and impact the researchers and industrialists in the field of biosorption seeking for economical, greener, and sustainable means to recover REEs.

Seasonal formation and stability of dissolved metal particles in mining-impacted, lacustrine sediments.

Formation of dissolved metal particles (<450 nm) in mining-impacted environments is a concern because of their potential for greater mobility and ecotoxicity compared to free ion and(or) sediment-bound metals. Metal-contaminated environments may produce soluble metal(loid) particles whose stability and transportability are determined by environmental conditions and particle composition. The Coeur d'Alene River Basin of northern Idaho, USA, is impacted by legacy mine waste-estimated 56 million tonnes of waste rock containing 900,000 t of Pb and 700,000 t of Zn were discharged into the Coeur d'Alene River and its tributaries during mining of argentiferous galena-sphalerite deposits. These legacy disposal practices resulted in substantial metal contamination-including As, Cd, Fe, Pb, Mn, and Zn-of floodplain sediments. Monthly lakewater samples and sediment cores were collected along the shoreline of a metal-contaminated lateral lake of the Coeur d'Alene River. Porewater was extracted from upper and lower sediments to evaluate the formation and stability of dissolved metal particles during seasonal changes. Substantial concentrations of Fe, Pb, Mn, and Zn were present in 450-nm filtered porewater during each month, with variable increases and decreases of metal concentrations in filtered lakewater according to seasonal changes. Dissolved metal particles with an average diameter of 180 ±â€¯115 nm were present in the porewater of the upper and lower sediments with size increases in early spring and decreases in fall. Particles in the lower sediment porewater were typically more stable, as indicated by more negative ζ potential values, and the greatest particle stability occurred during summer. Differences between upper and lower porewater metal particles correspond to changes in sediment S speciation and bond relocation resulting from an input of oxygenated groundwater. Transport of the dissolved metal particles in and from the sediments likely occurs with a change in the hydraulic gradient during a spring-to-summer transition that induces redox changes and increases particle stability. The presence of mining-related minerals and seasonal changes in environmental conditions allow for formation of dissolved metal particles, but the limited stability of the particles and/or low permeability of the sediments appear to limit, but not fully restrict, possible transport of metal particles to the overlying lakewater.

The synthesis and crystal structure of bis-[3,3-diethyl-1-(phenyl-imino-κN)thio-urea-κS]silver hexa-fluorido-phosphate.

The structure of the title complex, [Ag(C11H15N3S)2]PF6, has monoclinic (P21/c) symmetry, and the silver atom has a distorted square-planar geometry. The coordination complex crystallized from mixing silver hexa-fluorido-phosphate with a concentrated tetra-hydro-furan solution of N,N-di-ethyl-phenyl-azo-thio-formamide [ATF; systematic name: 3,3-diethyl-1-(phenyl-imino)-thio-urea] under ambient conditions. The resultant coordination complex exhibits a 2:1 ligand-to-metal ratio, with the silver(I) atom having a fourfold AgN2S2 coordination sphere, with a single PF6 counter-ion. In the crystal, however, one sulfur atom from an ATF ligand of a neighboring complex coordinates to the silver atom, with a bond distance of 2.9884 (14) Å. This creates a polymeric zigzag chain propagating along the c-axis direction. The chains are linked by C-H⋯F hydrogen bonds, forming slabs parallel to the ac plane.

Determining the Reliability of Measuring Mercury Cycling Gene Abundance with Correlations with Mercury and Methylmercury Concentrations.

Methylmercury (MeHg) is a bioaccumulative toxic contaminant in many ecosystems, but factors governing its production are poorly understood. Recent work has shown that the anaerobic microbial conversion of mercury (Hg) to MeHg requires the Hg-methylation genes hgcAB and that these genes can be used as biomarkers in PCR-based estimators of Hg-methylator abundance. In an effort to determine reliable methods for assessing hgcA abundance and diversity and linking them to MeHg concentrations, multiple approaches were compared including metagenomic shotgun sequencing, 16S rRNA gene pyrosequencing and cloning/sequencing hgcAB gene products. Hg-methylator abundance was also determined by quantitative hgcA qPCR amplification and metaproteomics for comparison to the above measurements. Samples from eight sites were examined covering a range of total Hg (HgT; 0.03-14 mg kg-1 dry wt. soil) and MeHg (0.05-27 µg kg-1 dry wt. soil) concentrations. In the metagenome and amplicon sequencing of hgcAB diversity, the Deltaproteobacteria were the dominant Hg-methylators while Firmicutes and methanogenic Archaea were typically ∼50% less abundant. This was consistent with metaproteomics estimates where the Deltaproteobacteria were steadily higher. The 16S rRNA gene pyrosequencing did not have sufficient resolution to identify hgcAB+ species. Metagenomic and hgcAB results were similar for Hg-methylator diversity and clade-specific qPCR-based approaches for hgcA are only appropriate when comparing the abundance of a particular clade across various samples. Weak correlations between Hg-methylating bacteria and soil Hg concentrations were observed for similar environmental samples, but overall total Hg and MeHg concentrations poorly correlated with Hg-cycling genes.

Key features and updates for origin 2018.

OriginLab's newest version update to Origin and OriginPro includes ease-of-use features, like Origin Central updates and creation of an App Center, as well as larger changes like the addition of Unicode characters, alteration to how user files are stored and visually searched, and user input formula in cells within worksheets. These features add additional value to an already powerful data analysis and plotting software package.

Carbon Amendments Alter Microbial Community Structure and Net Mercury Methylation Potential in Sediments.

Neurotoxic methylmercury (MeHg) is produced by anaerobic Bacteria and Archaea possessing the genes hgcAB, but it is unknown how organic substrate and electron acceptor availability impacts the distribution and abundance of these organisms. We evaluated the impact of organic substrate amendments on mercury (Hg) methylation rates, microbial community structure, and the distribution of hgcAB+ microbes with sediments. Sediment slurries were amended with short-chain fatty acids, alcohols, or a polysaccharide. Minimal increases in MeHg were observed following lactate, ethanol, and methanol amendments, while a significant decrease (∼70%) was observed with cellobiose incubations. Postincubation, microbial diversity was assessed via 16S rRNA amplicon sequencing. The presence of hgcAB+ organisms was assessed with a broad-range degenerate PCR primer set for both genes, while the presence of microbes in each of the three dominant clades of methylators (Deltaproteobacteria, Firmicutes, and methanogenic Archaea) was measured with clade-specific degenerate hgcA quantitative PCR (qPCR) primer sets. The predominant microorganisms in unamended sediments consisted of Proteobacteria, Firmicutes, Bacteroidetes, and Actinobacteria Clade-specific qPCR identified hgcA+Deltaproteobacteria and Archaea in all sites but failed to detect hgcA+Firmicutes Cellobiose shifted the communities in all samples to ∼90% non-hgcAB-containing Firmicutes (mainly Bacillus spp. and Clostridium spp.). These results suggest that either expression of hgcAB is downregulated or, more likely given the lack of 16S rRNA gene presence after cellobiose incubation, Hg-methylating organisms are largely outcompeted by cellobiose degraders or degradation products of cellobiose. These results represent a step toward understanding and exploring simple methodologies for controlling MeHg production in the environment.IMPORTANCE Methylmercury (MeHg) is a neurotoxin produced by microorganisms that bioacummulates in the food web and poses a serious health risk to humans. Currently, the impact that organic substrate or electron acceptor availability has on the mercury (Hg)-methylating microorganisms is unclear. To study this, we set up microcosm experiments exposed to different organic substrates and electron acceptors and assayed for Hg methylation rates, for microbial community structure, and for distribution of Hg methylators. The sediment and groundwater was collected from East Fork Poplar Creek in Oak Ridge, TN. Amendment with cellobiose (a lignocellulosic degradation by-product) led to a drastic decrease in the Hg methylation rate compared to that in an unamended control, with an associated shift in the microbial community to mostly nonmethylating Firmicutes This, along with previous Hg-methylating microorganism identification methods, will be important for identifying strategies to control MeHg production and inform future remediation strategies.

Deconvoluting the Innocent vs. Non-innocent Behavior of N,N-diethylphenylazothioformamide Ligands with Copper Sources.

Redox-active ligands lead to ambiguity in often clearly defined oxidation states of both the metal centre and the ligand. The arylazothioformamide (ATF) ligand class represents a redox-active ligand with three possible redox states (neutral, singly reduced, and doubly reduced). ATF-metal interactions result in strong colorimetric transitions allowing for the use of ATFs in metal detection and/or separations. While previous reports have discussed dissolution of zerovalent metals, the resulting oxidation states of coordination complexes have proved difficult to interpret through X-ray crystallographic analysis alone. This report describes the X-ray crystallographic analysis combined with computational modelling of the ATF ligand and metal complexes to deconvolute the metal and ligand oxidation state of metal-ATF complexes. Metal(ATF)2 complexes that originated from zerovalent metals were found to exist as dicationic metal centers containing two singly reduced ATF ligands. When employing Cu(I) salts instead of Cu(0) to generate copper-ATF complexes, the resulting complexes remained Cu(I) and the ATF ligand remained "innocent", existing in its neutral state. Although the use of CuX (where X = Br or I) or [Cu(NCMe)4]Y (where Y = BF4 or PF6) generated species of the type: [(ATF)Cu(µ-X)]2 and [Cu(ATF)2]Y, respectively, the ATF ligand remained in its neutral state for each species type.

Improved yield of high molecular weight DNA coincides with increased microbial diversity access from iron oxide cemented sub-surface clay environments.

Despite over three decades of progress, extraction of high molecular weight (HMW) DNA from high clay soils or iron oxide cemented clay has remained challenging. HMW DNA is desirable for next generation sequencing as it yields the most comprehensive coverage. Several DNA extraction procedures were compared from samples that exhibit strong nucleic acid adsorption. pH manipulation or use of alternative ion solutions offered no improvement in nucleic acid recovery. Lysis by liquid N2 grinding in concentrated guanidine followed by concentrated sodium phosphate extraction supported HMW DNA recovery from clays high in iron oxides. DNA recovered using 1 M sodium phosphate buffer (PB) as a competitive desorptive wash was 15.22±2.33 µg DNA/g clay, with most DNA consisting of >20 Kb fragments, compared to 2.46±0.25 µg DNA/g clay with the Powerlyzer system (MoBio). Increasing PB concentration in the lysis reagent coincided with increasing DNA fragment length during initial extraction. Rarefaction plots of 16S rRNA (V1-V3 region) pyrosequencing from A-horizon and clay soils showed an ∼80% and ∼400% larger accessed diversity compared to the Powerlyzer soil DNA system, respectively. The observed diversity from the Firmicutes showed the strongest increase with >3-fold more operational taxonomic units (OTU) recovered.

Role of morphological growth state and gene expression in Desulfovibrio africanus strain Walvis Bay mercury methylation.

The biogeochemical transformations of mercury are a complex process, with the production of methylmercury, a potent human neurotoxin, repeatedly demonstrated in sulfate- and Fe(III)-reducing as well as methanogenic bacteria. However, little is known regarding the morphology, genes, or proteins involved in methylmercury generation. Desulfovibrio africanus strain Walvis Bay is a Hg-methylating δ-proteobacterium with a sequenced genome and has unusual pleomorphic forms. In this study, a relationship between the pleomorphism and Hg methylation was investigated. Proportional increases in the sigmoidal (regular) cell form corresponded with increased net MeHg production but decreased when the pinched cocci (persister) form became the major morphotype. D. africanus microarrays indicated that the ferrous iron transport genes (feoAB), as well as ribosomal genes and several genes whose products are predicted to have metal binding domains (CxxC), were up-regulated during exposure to Hg in the exponential phase. Whereas no specific methylation pathways were identified, the finding that Hg may interfere with iron transport and the correlation of growth-phase-dependent morphology with MeHg production are notable. The identification of these relationships between differential gene expression, morphology, and the growth-phase dependence of Hg transformations suggests that actively growing cells are primarily responsible for methylation, and so areas with ample carbon and electron-acceptor concentrations may also generate a higher proportion of methylmercury than more oligotrophic environments. The observation of increased iron transporter expression also suggests that Hg methylation may interfere with iron biogeochemical cycles.

Microbial community succession during lactate amendment and electron acceptor limitation reveals a predominance of metal-reducing Pelosinus spp.

The determination of the success of in situ bioremediation strategies is complex. By using controlled laboratory conditions, the influence of individual variables, such as U(VI), Cr(VI), and electron donors and acceptors on community structure, dynamics, and the metal-reducing potential can be studied. Triplicate anaerobic, continuous-flow reactors were inoculated with Cr(VI)-contaminated groundwater from the Hanford, WA, 100-H area, amended with lactate, and incubated for 95 days to obtain stable, enriched communities. The reactors were kept anaerobic with N(2) gas (9 ml/min) flushing the headspace and were fed a defined medium amended with 30 mM lactate and 0.05 mM sulfate with a 48-h generation time. The resultant diversity decreased from 63 genera within 12 phyla to 11 bacterial genera (from 3 phyla) and 2 archaeal genera (from 1 phylum). Final communities were dominated by Pelosinus spp. and to a lesser degree, Acetobacterium spp., with low levels of other organisms, including methanogens. Four new strains of Pelosinus were isolated, with 3 strains being capable of Cr(VI) reduction while one also reduced U(VI). Under limited sulfate, it appeared that the sulfate reducers, including Desulfovibrio spp., were outcompeted. These results suggest that during times of electron acceptor limitation in situ, organisms such as Pelosinus spp. may outcompete the more-well-studied organisms while maintaining overall metal reduction rates and extents. Finally, lab-scale simulations can test new strategies on a smaller scale while facilitating community member isolation, so that a deeper understanding of community metabolism can be revealed.

Simultaneous leaching and carbon sequestration in constrained aqueous solutions.

The behavior of metal ions' leaching and precipitated mineral phases of metal-rich fly ash (FA) was examined in order to evaluate microbial impacts on carbon sequestration and metal immobilization. The leaching solutions consisted of aerobic deionized water (DW) and artificial eutrophic water (AEW) that was anaerobic, organic- and mineral-rich, and higher salinity as is typical of bottom water in eutrophic algae ponds. The Fe- and Ca-rich FAs were predominantly composed of quartz, mullite, portlandite, calcite, hannebachite, maghemite, and hematite. After 86 days, only Fe and Ca contents exhibited a decrease in leaching solutions while other major and trace elements showed increasing or steady trends in preference to the type of FA and leaching solution. Ca-rich FA showed strong carbon sequestration efficiency ranging up to 32.3 g CO(2)/kg FA after 86 days, corresponding to almost 65% of biotic carbon sequestration potential under some conditions. Variations in the properties of FAs such as chemical compositions, mineral constituents as well as the type of leaching solution impacted CO(2) capture. Even though the relative amount of calcite increased sixfold in the AEW and the relative amount of mineral phase reached 37.3 wt% using Ca-rich FA for 86 days, chemical sequestration did not accomplish simultaneous precipitation and sequestration of several heavy metals.

Influence of pH and inorganic phosphate on toxicity of zinc to Arthrobacter sp. isolated from heavy-metal-contaminated sediments.

Because of its high solubility over a wide range of pH conditions, zinc is found in many natural and human-impacted systems. Zinc speciation is critical in assessing zinc toxicity to microorganisms because it varies considerably with pH and is dependent on other aqueous constituents. Combined results of thermodynamic modeling, statistical analysis, and batch culture studies using Arthrobacter sp. JM018 suggest that the toxic species may not be solely limited to the free ion, but also includes ZnHPO(4)(0)(aq). Cellular uptake of ZnHPO(4)(0)(aq) through the inorganic phosphate transporter (Pit family), which requires a neutral metal phosphate complex for phosphate transport, may explain the observed toxicity. Based on visual MINTEQ (v3.0) modeling, at 50 µM total zinc, ZnHPO(4)(0)(aq) constitutes 33, 70, and 76% of the neutral metal phosphate pool at pH 6, 7, and 8, respectively. At 50 µM total zinc, cultures supplied with organic phosphate (glycerol-3-phosphate) show no significant response to pH (p = 0.13) while inhibition of inorganic phosphate-supplemented cultures, whose neutral metal phosphates are increasingly dominated by ZnHPO(4)(0)(aq), show significant pH dependence (p = 9.45 × 10(-7)). Using sodium to decrease the distribution of ZnHPO(4)(0)(aq) in the neutral metal phosphate pool also decreased the pH dependent toxicity, further supporting this mechanism. These findings show the important role of minor zinc species in organism toxicity and have wider implications because the Pit inorganic phosphate transport system is widely distributed in Bacteria, Archaea, and Eukarya.

The toxicity of lead to Desulfovibrio desulfuricans G20 in the presence of goethite and quartz.

An aqueous mixture of goethite, quartz, and lead chloride (PbCl(2)) was treated with the sulfate-reducing bacterium, Desulfovibrio desulfuricans G20 (D. desulfuricans G20), in a medium specifically designed to assess metal toxicity. In the presence of 26 muM of soluble Pb, together with the goethite and quartz, D. desulfuricans G20 grew after a lag time of 5 days compared to 2 days in Pb-, goethite-, and quartz-free treatments. In the absence of goethite and quartz, however, with 26 microM soluble Pb, no measurable growth was observed. Results showed that D. desulfuricans G20 first removed Pb from solutions then growth began resulting in black precipitates of Pb and iron sulfides. Transmission electron microscopic analyses of thin sections of D. desulfuricans G20 treated with 10 microM PbCl(2) in goethite- and quartz-free treatment showed the presence of a dense deposit of lead sulfide precipitates both in the periplasm and cytoplasm. However, thin sections of D. desulfuricans G20 treated with goethite, quartz, and PbCl(2) (26 microM soluble Pb) showed the presence of a dense deposit of iron sulfide precipitates both in the periplasm and cytoplasm. Energy-dispersive X-ray spectroscopy, selected area electron diffraction patterns, or X-ray diffraction analyses confirmed the structure of precipitated Pb inside the cell as galena (PbS) in goethite- and quartz-free treatments, and iron sulfides in treatments with goethite, quartz, and PbCl(2). Overall results suggest that even at the same soluble Pb concentration (26 microM), in the presence of goethite and quartz, apparent Pb toxicity to D. desulfuricans G20 decreased significantly. Further, accumulation of lead/iron sulfides inside D. desulfuricans G20 cells depended on the presence of goethite and quartz.

Molecular studies on the microbial diversity associated with mining-impacted Coeur d'Alene River sediments.

The prokaryotic diversity associated with highly metal-contaminated sediment samples collected from the Coeur d'Alene River (CdAR) was investigated using a cultivation-independent approach. Bacterial community structure was studied by constructing an RNA polymerase beta subunit (rpoB) gene library. Phylogenetic analysis revealed that 75.8% of the rpoB clones were associated with beta-Proteobacteria while the remaining 24.2% were with gamma-Proteobacteria. All phylotypes showed close similarity to previously reported cultivable lineages from metal or organic contaminant-rich environments. In an archaeal 16S rRNA gene library, 70% of the clones were affiliated to Crenarchaeota, while 30% belonged to Euryarchaeota. Most of the Euryarchaeota sequences were related to acetoclastic lineages belonging to Methanosarcinales. A single phylotype within the Euryarchaeota showed no association with cultivable euryarchaeotal lineages and might represent novel taxon. Diversity indices demonstrated greater diversity of Bacteria compared to Archaea in CdAR sediments. Sediment characterization by the X-ray fluorescence spectroscopy revealed high amount of toxic metals. To our knowledge, this is the first culture-independent survey on the prokaryotic diversity present in mining-impacted sediments of CdAR.