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Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [ε] = −0.4 to −1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (∼10-nm diameter by 200-nm length), which cluster together, forming larger (∼1,000-nm) rosettes composed of numerous individual shards (∼100-nm width by 1,000-nm length). In contrast, Sulfurospirillum barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods.

Applied and Environmental Microbiology

Investigation into the effect of heteroatom content on kerogen structure using advanced 13C solid-state nuclear magnetic resonance spectroscopy

To elucidate how different extreme heteroatom concentrations in oil shale kerogen may present and contribute to various structural features, three shale samples, containing kerogen with high oxygen content, low heteroatom content, and high sulfur content, were analyzed using advanced 13 C solid-state nuclear magnetic resonance (NMR) techniques, including multiple cross-polarization/magic angle spinning (multiCP/MAS), dipolar dephasing (multiCP/DD), and 2D 1 H– 13 C heteronuclear correlation (2D HETCOR). We found that oxygen in Estonian kukersite was present mostly in aromatic C–O structures and that nonprotonated aromatic carbons bonded to oxygen and alkyl chains led to more diverse aromatic signal distributions and structures in the kukersite organic matter than were observed in the other shales. The low-heteroatom kerogen present in Australian Glen Davis torbanite had the simplest structural pattern and the lowest aromaticity, despite having a lower atomic H/C ratio than the kerogens present in the other shales. The organic sulfur-rich Ghareb marinite from Jordan contained the highest aromaticity and most diverse alkyl structures among the three shales. 2D HETCOR with 1 H spin diffusion showed that the structural heterogeneity of the Glen Davis kerogen was <1 nm, indicating the preservation of structures present in precursor organic matter. Like previous NMR studies of shales and kerogens, this analysis of organic matter in whole shale samples with unusual heteroatom content demonstrates that structural characteristics in organic matter are not necessarily captured by kerogen typing based solely on elemental ratios (H/C, O/C) or programmed pyrolysis parameters and that NMR provides deeper insights into kerogen structure.

Energy & Fuels

Statistical evaluation of an inductively coupled plasma atomic emission spectrometric method for routine water quality testing

In an interlaboratory test, inductively coupled plasma atomic emission spectrometry (ICP-AES) was compared with flame atomic absorption spectrometry and molecular absorption spectrophotometry for the determination of 17 major and trace elements in 100 filtered natural water samples. No unacceptable biases were detected. The analysis precision of ICP-AES was found to be equal to or better than alternative methods. Known-addition recovery experiments demonstrated that the ICP-AES determinations are accurate to between plus or minus 2 and plus or minus 10 percent; four-fifths of the tests yielded average recoveries of 95-105 percent, with an average relative standard deviation of about 5 percent.

Applied Spectroscopy

Characterization of the partial oxidation products of crude oil contaminating groundwater at the U.S. Geological Survey Bemidji research site in Minnesota by elemental analysis, radiocarbon dating, nuclear magnetic resonance spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry

In oil spill research, a topic of increasing attention during the last decade has been the environmental impact of the partial oxidation products that result from transformation of the petroleum in freshwater, marine, and terrestrial ecosystems. This report describes the isolation and characterization of the partial oxidation products from crude oil contaminating groundwater at the long-term U.S. Geological Survey Bemidji research site in Minnesota. As the result of a pipeline burst in August 1979, a body of light aliphatic crude oil is present from the land surface to 2 meters below the water table in a shallow sand and gravel aquifer in a remote area outside Bemidji, Minnesota, United States. Biodegradation has resulted in the formation of a plume of dissolved organic carbon (DOC) downgradient from the oil body. Groundwater has also been contaminated in an area known as the spray zone, from vertical infiltration of DOC resulting from biodegradation of oil in the soil column, and possibly from photooxidation of oil at the soil surface. The majority of DOC in the contaminated groundwater is in the form of nonvolatile organic acids (NVOAs) which represent the partial oxidation products of the crude oil constituents. The NVOAs have been classified into three fractions according to their isolation on XAD resins: hydrophobic neutrals (HPON), hydrophobic acids (HPOA), and hydrophilic acids (HPIA). These fractions of NVOAs were isolated from wells downgradient from the oil body (sampling well numbers 533, 532, 530, 515), in the spray zone (603), and from an uncontaminated well upgradient of the oil body (310) between the years 1986 and 1989, and again from wells 530 and 603 in 1998. The samples have been characterized by elemental analysis, radiocarbon dating, carbon-13 nuclear magnetic resonance spectroscopy ( 13 C NMR), and negative-mode (-) electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS), with a particular focus on fractions from wells 310, 530, and 603. All the characterization data indicate that the NVOAs from contaminated wells are distinguishable from the background DOC. Carbon-14 ( 14 C) ages of NVOAs from contaminated wells ranged from 3,615 to 18,985 years before the present, whereas the background DOC from the aquifer was post-bomb (post 1950). By elemental analysis, NVOAs from contaminated wells had higher sulfur but lower nitrogen contents than the background. By electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, number average molecular weights determined from assigned molecular formulas ranged from 416 to 486 daltons for the HPOA and HPIA fractions from both background and contaminant wells. NVOAs from contaminated wells had significantly greater numbers of assigned molecular formulas containing sulfur, with elevated concentrations of the S 1 O 4-10 species in particular. Compared to the background, HPOA and HPIA fractions from contaminant wells had a broader range of double bond equivalents (DBEs) within O n compound classes (n is number of atoms). Additionally, within O n compound classes, contaminant well HPOA fractions had a greater abundance of lower n (less than eight) than the background. Contaminant well double bond equivalents versus carbon number (C # ) plots of oxygen compound classes suggest oil-derived aliphatic compounds in the range from C 12 to C 22 in HPOA and HPIA fractions and oil-derived compounds containing aromatic or saturated rings in the approximate range from C 20 to C 30 are present in HPOA fractions. The data suggest the NVOAs originate from biodegradation of several classes of C 12 and greater crude oil constituents: sulfur-containing constituents, including possibly the resins and asphaltenes; constituents containing aromatic rings substituted with methyl groups, including alkylaromatic and naph- thenoaromatic compounds, and C 12 to C 22 alkyl constituents. The overall similarities of the carbon-13 nuclear magnetic resonance spectra for the well 603 and 530 samples from the two sampling dates suggest that a steady state in the composition of the partial oxidation products in each of the two wells had been reached between 1986–1989 and 1998.

Minnesota

Complex carbonate ore mineralogy in the Mountain Pass carbonatite rare earth element deposit, USA

Economic concentrations of rare earth element (REE) minerals are uncommon in the Earth’s crust, with most occurring in carbonatites. Unlike most igneous rocks composed of silicate minerals, carbonatites are dominated by carbonate minerals, some of which can incorporate significant light REEs (LREEs; La, Ce, Pr, Nd). Technological applications of REEs are numerous and they have been identified as some of the most critical mineral commodities to the global economy. The Mountain Pass carbonatite stock in the Mojave Desert of California is the most economically significant REE deposit in the USA and contains a few to tens of percent (by volume) of the carbonate REE ore mineral bastnäsite. Despite the economic significance of the Mountain Pass deposit, studies of its ore mineralogy are limited. Here we present new carbonate ore mineralogy data for a compositionally diverse suite of carbonatitic rocks from the Mountain Pass stock and related dikes. Whole-rock geochemical data are integrated with mineral-scale textural and chemical data obtained by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and microRaman spectroscopy. Our results document a complex spectrum of REE-bearing carbonate minerals and intermediate mixed-layer structures. Mineral species include bastnäsite [REE(CO 3 )F], hydroxylbastnäsite [REE(CO 3 )OH], parisite [Ca(REE) 2 (CO 3 ) 3 F 2 ], synchysite [Ca(REE)(CO 3 ) 2 F], röntgenite [Ca 2 (Ce,La) 3 (CO 3 ) 5 F 3 ], and sahamalite [(Mg,Fe 2+ )(REE) 2 (CO 3 ) 4 ]. Carbonate ore mineralogy is heterogeneous within and between samples, including at the intracrystal scale. Complexly zoned crystals exhibit as many as five to six different compositional domains and syntaxial intergrowths, commonly with the more Ca-rich varieties (parisite, synchysite) forming crystal rims that surround relict bastnäsite cores. We attribute the phenocryst variability to changes in the chemistry and temperature of primary carbonatite magmas and evolved/exsolved fluids. Cross-cutting vein textures of calcite, celestine and various REE carbonate minerals, interstitial bastnäsite crystallization, breccia blocks lined by fine-grained bastnäsite, and the presence of hydroxylbastnäsite and partially hydroxylated bastnäsite point to the role of secondary hydrothermal processes in REE mineralization. Fluorcarbonate mineral compositions demonstrate that La and Ce are more structurally abundant in bastnäsite, whereas the more Ca-rich species (parisite, synchysite) contain a greater proportion of REE heavier than Pr (Nd, Sm, Eu, Gd) and Y. Atomic ratios of Pr/(Nd + Pr) are likewise variable, with the highest average value for bastnäsite (0.25) compared to parisite (0.22) and sychysite (0.21). This finding has geometallurgical implications, given that current mining operations are focused on recovery of Nd and Pr for high field strength permanent magnets and the Nd/Pr ratios are a critical factor in ore processing and magnet manufacture.

California

Aluminosilicate melts and glasses at 1 to 3 GPa: Temperature and pressure effects on recovered structural and density changes

In the pressure range in the Earth&rsquo;s mantle where many basaltic magmas are generated (1 to 3 GPa) (Stolper et al. 1981), increases in the coordination numbers of the network-forming cations in aluminosilicate melts have generally been considered to be minor, although effects on silicon and particularly on aluminum coordination in non-bridging oxygen-rich glasses from the higher, 5 to 12 GPa range, are now well known. Most high-precision measurements of network cation coordination in such samples have been made by spectroscopy (notably 27 Al and 29 Si NMR) on glasses quenched from high-temperature, high-pressure melts synthesized in solid-media apparatuses and decompressed to room temperature and 1 bar pressure. There are several effects that could lead to the underestimation of the extent of actual structural (and density) changes in high-pressure/temperature melts from such data. For non-bridging oxygen-rich sodium and calcium aluminosilicate compositions in the 1 to 3 GPa range, we show here that glasses annealed near to their glass transition temperatures systematically record higher recovered increases in aluminum coordination and in density than samples quenched from high-temperature melts. In the piston-cylinder apparatus used, rates of cooling through the glass transition are measured as very similar for both higher and lower initial temperatures, indicating that fictive temperature effects are not the likely explanation of these differences. Instead, transient decreases in melt pressure during thermal quenching, which may be especially large for high initial run temperatures, of as much as 0.5 to 1 GPa, may be responsible. As a result, the equilibrium proportion of high-coordinated Al in this pressure range may be 50 to 90% greater than previously estimated, reaching mean coordination numbers (e.g., 4.5) that are probably high enough to significantly affect melt properties. New data on jadeite (NaAlSi 2 O 6 ) glass confirm that aluminum coordination increase with pressure is inhibited in compositions low in non-bridging O atoms.

American Mineralogist

ChemCam activities and discoveries during the nominal mission of the Mars Science Laboratory in Gale crater, Mars

At Gale crater, Mars, ChemCam acquired its first laser-induced breakdown spectroscopy (LIBS) target on Sol 13 of the landed portion of the mission (a Sol is a Mars day). Up to Sol 800, more than 188 000 LIBS spectra were acquired on more than 5800 points distributed over about 650 individual targets. We present a comprehensive review of ChemCam scientific accomplishments during that period, together with a focus on the lessons learned from the first use of LIBS in space. For data processing, we describe new tools that had to be developed to account for the uniqueness of Mars data. With regard to chemistry, we present a summary of the composition range measured on Mars for major-element oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O) based on various multivariate models, with associated precisions. ChemCam also observed H, and the non-metallic elements C, O, P, and S, which are usually difficult to quantify with LIBS. F and Cl are observed through their molecular lines. We discuss the most relevant LIBS lines for detection of minor and trace elements (Li, Rb, Sr, Ba, Cr, Mn, Ni, and Zn). These results were obtained thanks to comprehensive ground reference datasets, which are set to mimic the expected mineralogy and chemistry on Mars. With regard to the first use of LIBS in space, we analyze and quantify, often for the first time, each of the advantages of using stand-off LIBS in space: no sample preparation, analysis within its petrological context, dust removal, sub-millimeter scale investigation, multi-point analysis, the ability to carry out statistical surveys and whole-rock analyses, and rapid data acquisition. We conclude with a discussion of ChemCam performance to survey the geochemistry of Mars, and its valuable support of decisions about selecting where and whether to make observations with more time and resource-intensive tools in the rover's instrument suite. In the end, we present a bird's-eye view of the many scientific results: discovery of felsic Noachian crust, first observation of hydrated soil, discovery of manganese-rich coatings and fracture fills indicating strong oxidation potential in Mars' early atmosphere, characterization of soils by grain size, and wide scale mapping of sedimentary strata, conglomerates, and diagenetic materials.

Journal of Analytical Atomic Spectrometry