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USGS2012

The effect of nonylphenol on gene expression in Atlantic salmon smolts

The parr–smolt transformation in Atlantic salmon (Salmo salar) is a complex developmental process that culminates in the ability to migrate to and live in seawater. Exposure to environmental contaminants like nonylphenol can disrupt smolt development and may be a contributing factor in salmon population declines. We used GRASP 16K cDNA microarrays to investigate the effects of nonylphenol on gene expression in Atlantic salmon smolts. Nonylphenol exposure reduced gill Na+/K+-ATPase activity and plasma cortisol and triiodothyronine levels. Transcriptional responses were examined in gill, liver, olfactory rosettes, hypothalamus, and pituitary. Expression of 124 features was significantly altered in the liver of fish exposed to nonylphenol; little to no transcriptional effects were observed in other tissues. mRNA abundance of genes involved in protein biosynthesis, folding, modification, transport and catabolism; nucleosome assembly, cell cycle, cell differentiation, microtubule-based movement, electron transport, and response to stress increased in nonylphenol-treated fish. This study expands our understanding of the effect of nonylphenol on smolting and provides potential targets for development of biomarkers.

Aquatic Toxicology↗

USGS2005

X-ray scattering and spectroscopy studies on diesel soot from oxygenated fuel under various engine load conditions

Diesel soot from reference diesel fuel and oxygenated fuel under idle and load engine conditions was investigated with X-ray scattering and X-ray carbon K-edge absorption spectroscopy. Up to five characteristic size ranges were found. Idle soot was generally found to have larger primary particles and aggregates but smaller crystallites, than load soot. Load soot has a higher degree of crystallinity than idle soot. Adding oxygenates to diesel fuel enhanced differences in the characteristics of diesel soot, or even reversed them. Aromaticity of idle soot from oxygenated diesel fuel was significantly larger than from the corresponding load soot. Carbon near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was applied to gather information about the presence of relative amounts of carbon double bonds (CC, CO) and carbon single bonds (C-H, C-OH, COOH). Using scanning X-ray transmission microspectroscopy (STXM), the relative amounts of these carbon bond states were shown to vary spatially over distances approximately 50 to 100 nm. The results from the X-ray techniques are supported by thermo-gravimetry analysis and high-resolution transmission electron microscopy. ?? 2005 Elsevier Ltd. All rights reserved.

Carbon↗

USGS2004

Using magnetic susceptibility to facilitate more rapid, reproducible and precise delineation of hydric soils in the midwestern USA

Standard field indicators, currently used for hydric soil delineations [USDA-NRCS, 1998. Field indicators of hydric soils in the United States, Version 4.0. In: G.W. Hurt et al. (Ed.), United States Department of Agriculture-NRCS, Fort Worth, TX], are useful, but in some cases, they can be subjective, difficult to recognize, or time consuming to assess. Magnetic susceptibility (MS) measurements, acquired rapidly in the field with a portable meter, have great potential to help soil scientists delineate and map areas of hydric soils more precisely and objectively. At five sites in Illinois (from 5 to 15 ha in area) with contrasting soil types and glacial histories, the MS values of surface soils were measured along transects, and afterwards mapped and contoured. The MS values were found to be consistently higher in well-drained soils and lower in hydric soils, reflecting anaerobic deterioration of both detrital magnetite and soil-formed ferrimagnetics. At each site, volumetric MS values were statistically compared to field indicators to determine a critical MS value for hydric soil delineation. Such critical values range between 22??10-5 and 33??10-5 SI in silty loessal or alluvial soils in Illinois, but are as high as 61??10-5 SI at a site with fine sandy soil. A higher magnetite content and slower dissolution rate in sandy soils may explain the difference. Among sites with silty parent material, the lowest critical value (22??10-5 SI) occurs in soil with low pH (4.5-5.5) since acidic conditions are less favorable to ferrimagnetic mineral neoformation and enhance magnetite dissolution. Because of their sensitivity to parent material properties and soil pH, critical MS values must be determined on a site specific basis. The MS of studied soil samples (0-5 cm depth) is mainly controlled by neoformed ultrafine ferrimagnetics and detrital magnetite concentrations, with a minor contribution from anthropogenic fly ash. Neoformed ferrimagnetics are present in all samples but, based on high ??FD% (???5% to 10%), are most prevalent in high pH Mollisols of northeastern Illinois. Scanning electron microscope images display significantly more detrital magnetite alteration in hydric soils, substantiating that reductive dissolution of magnetite (aided by microorganisms) is a primary cause for lower MS. Fly ash comprises 8-50% of the >5 ??m strongly magnetic particles and typically accounts for 5-15% of the total MS signal. The proportion of fly ash in >5 ??m strongly magnetic fractions is greater in hydric soils because of lower natural magnetite contents, possibly combined with historical topsoil accumulation in lower landscapes. Magnetic fly ash particles are also more altered in low MS soils, implying that significant magnetite dissolution can occur in less than 150 years. ?? 2004 Elsevier B.V. All rights reserved.

Catena↗

USGS2012

Transcriptional profiling of the parr–smolt transformation in Atlantic salmon

The parr–smolt transformation in Atlantic salmon ( Salmo salar ) is a complex developmental process that culminates in the ability to migrate to and live in seawater. We used GRASP 16K cDNA microarrays to identify genes that are differentially expressed in the liver, gill, hypothalamus, pituitary, and olfactory rosettes of smolts compared to parr. Smolts had higher levels of gill Na + /K + -ATPase activity, plasma cortisol and plasma thyroid hormones relative to parr. Across all five tissues, stringent microarray analyses identified 48 features that were differentially expressed in smolts compared to parr. Using a less stringent method we found 477 features that were differentially expressed at least 1.2-fold in smolts, including 172 features in the gill. Smolts had higher mRNA levels of genes involved in transcription, protein biosynthesis and folding, electron transport, oxygen transport, and sensory perception and lower mRNA levels for genes involved in proteolysis. Quantitative RT-PCR was used to confirm differential expression in select genes identified by microarray analyses and to quantify expression of other genes known to be involved in smolting. This study expands our understanding of the molecular processes that underlie smolting in Atlantic salmon and identifies genes for further investigation.

Comparative Biochemistry and Physiology, Part D: G↗

USGS2007

Hydrothermal nontronite formation at Eolo Seamount (Aeolian volcanic arc, Tyrrhenian Sea)

A sediment core containing a yellowish-green clay bed was recovered from an area of extensive hydrothermal deposition at the SE slope of the Eolo Seamount, Tyrrhenian Sea. The clay bed is composed of pure nontronite (described for the first time in the Tyrrhenian Sea), which appears to be the most aluminous nontronite ever found among the seafloor hydrothermal deposits. The high Al content suggests precipitation from Al-containing hydrothermal solutions. The REE distribution of the Eolo nontronite has a V-shape pattern. The heavy REE enrichment is in part due to their preferential partitioning in the nontronite structure. This enrichment was possibly further enhanced by the HREE preferential sorption on bacterial cell walls. The light REE enrichment is the result of scavenging uptake by one of the nontronite precursors, i.e., poorly-ordered Fe-oxyhydroxides, from the hydrothermal fluids. Oxygen isotopic composition of the nontronite yields a formation temperature of 30????C, consistent with a low-temperature hydrothermal origin. The relatively radiogenic Nd isotopic signature of the nontronite compared to the present-day Mediterranean seawater indicates that approximately half of Nd, and presumably the rest of the LREE, are derived from local volcanic sources. On the other hand, 87Sr/86Sr is dominated by present-day seawater Sr. Scanning electron microscopy investigation revealed that the nontronite is composed of aggregates of lepispheres and tube-like filaments, which are indicative of bacteria assisted precipitation. Bacteria inhabiting this hydrothermal site likely acted as reactive geochemical surfaces on which poorly-ordered hydrothermal Fe-oxyhydroxides and silica precipitated. Upon aging, the interactions of these primary hydrothermal precipitates coating bacterial filaments and cell walls likely led to the formation of nontronite. Finally, the well-balanced interlayer and layer charges of the crystal lattice of seafloor hydrothermal nontronite decrease its sorption capacity to zero. Thus the ubiquitous nontronite precipitation along the active plate boundaries and around the hot spots has no significant impact on oceanic trace element chemistry. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

Mineralogy and geochemistry of a superhigh-organic-sulfur coal, Yanshan Coalfield, Yunnan, China: Evidence for a volcanic ash component and influence by submarine exhalation

The mineralogy and geochemistry of a superhigh-organic-sulfur (SHOS) coal of Late Permian age from the Yanshan Coalfield, Yunnan Province, southwestern China, have been studied using optical microscope, low-temperature ashing plus X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, a sequential chemical extraction procedure, and inductively coupled plasma mass spectrometry. The M9 Coal from the Yanshan Coalfield is a SHOS coal that has a total sulfur content of 10.12%-11.30% and an organic sulfur content of 8.77%-10.30%. The minerals in the coal consist mainly of high-temperature quartz, sanidine, albite, muscovite, illite, pyrite, and trace amounts of kaolinite, plagioclase, akermanite, rutile, and dawsonite. As compared with ordinary worldwide (bituminous coals and anthracite) and Chinese coals, the M9 Coal is remarkably enriched in B (268????g/g), F (841????g/g), V (567????g/g), Cr (329????g/g), Ni (73.9????g/g), Mo (204????g/g), and U (153????g/g). In addition, elements including Se (25.2????g/g), Zr (262????g/g), Nb (20.1????g/g), Cd (2.07????g/g), and Tl (2.03????g/g) are also enriched in the coal. Occurrence of high-temperature quartz, sanidine, muscovite, and illite in the M9 Coal is evidence that there is a volcanic ash component in the coal that was derived from acid volcanic ashes fallen into the swamp during peat accumulation. Occurrence of albite and dawsonite in the coal and strong enrichment of some elements, including F, S, V, Cr, Ni, Mo and U, are attributed to the influence by submarine exhalation which invaded along with seawater into the anoxic peat swamp. Abundances of lithophile elements, including rare earth elements, Nb, Y, Zr, and TiO2, indicate that the silicate minerals in the coal were derived from the northern Vietnam Upland to the south of the basin. ?? 2008 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2009

In situ measurements of microbially-catalyzed nitrification and nitrate reduction rates in an ephemeral drainage channel receiving water from coalbed natural gas discharge, Powder River Basin, Wyoming, USA

Nitrification and nitrate reduction were examined in an ephemeral drainage channel receiving discharge from coalbed natural gas (CBNG) production wells in the Powder River Basin, Wyoming. CBNG co-produced water typically contains dissolved inorganic nitrogen (DIN), primarily as ammonium. In this study, a substantial portion of discharged ammonium was oxidized within 50 m of downstream transport, but speciation was markedly influenced by diel fluctuations in dissolved oxygen (> 300 µM). After 300 m of transport, 60% of the initial DIN load had been removed. The effect of benthic nitrogen-cycling processes on stream water chemistry was assessed at 2 locations within the stream channel using acrylic chambers to conduct short-term (2–6 h), in-stream incubations. The highest ambient DIN removal rates (2103 µmol N m − 2 h − 1 ) were found at a location where ammonium concentrations > 350 µM. This occurred during light incubations when oxygen concentrations were highest. Nitrification was occurring at the site, however, net accumulation of nitrate and nitrite accounted for < 12% of the ammonium consumed, indicating that other ammonium-consuming processes were also occurring. In dark incubations, nitrite and nitrate consumption were dominant processes, while ammonium was produced rather than consumed. At a downstream location nitrification was not a factor and changes in DIN removal rates were controlled by nitrate reduction, diel fluctuations in oxygen concentration, and availability of electron donor. This study indicates that short-term adaptation of stream channel processes can be effective for removing CBNG DIN loads given sufficient travel distances, but the long-term potential for nitrogen remobilization and nitrogen saturation remain to be determined.

Chemical Geology↗

USGS2010

In situ sulfur isotope analysis of sulfide minerals by SIMS: Precision and accuracy, with application to thermometry of ~3.5Ga Pilbara cherts

Secondary ion mass spectrometry (SIMS) measurement of sulfur isotope ratios is a potentially powerful technique for in situ studies in many areas of Earth and planetary science. Tests were performed to evaluate the accuracy and precision of sulfur isotope analysis by SIMS in a set of seven well-characterized, isotopically homogeneous natural sulfide standards. The spot-to-spot and grain-to-grain precision for δ34S is ± 0.3‰ for chalcopyrite and pyrrhotite, and ± 0.2‰ for pyrite (2SD) using a 1.6 nA primary beam that was focused to 10 µm diameter with a Gaussian-beam density distribution. Likewise, multiple δ34S measurements within single grains of sphalerite are within ± 0.3‰. However, between individual sphalerite grains, δ34S varies by up to 3.4‰ and the grain-to-grain precision is poor (± 1.7‰, n = 20). Measured values of δ34S correspond with analysis pit microstructures, ranging from smooth surfaces for grains with high δ34S values, to pronounced ripples and terraces in analysis pits from grains featuring low δ34S values. Electron backscatter diffraction (EBSD) shows that individual sphalerite grains are single crystals, whereas crystal orientation varies from grain-to-grain. The 3.4‰ variation in measured δ34S between individual grains of sphalerite is attributed to changes in instrumental bias caused by different crystal orientations with respect to the incident primary Cs+ beam. High δ34S values in sphalerite correlate to when the Cs+ beam is parallel to the set of directions < uuw>, from [111] to [110], which are preferred directions for channeling and focusing in diamond-centered cubic crystals. Crystal orientation effects on instrumental bias were further detected in galena. However, as a result of the perfect cleavage along {100} crushed chips of galena are typically cube-shaped and likely to be preferentially oriented, thus crystal orientation effects on instrumental bias may be obscured. Test were made to improve the analytical precision of δ34S in sphalerite, and the best results were achieved by either reducing the depth of the analysis pits using a Köhler illuminated primary beam, or by lowering the total impact energy from 20 keV to 13 keV. The resulting grain-to-grain precision in δ34S improves from ± 1.7‰ to better than 0.6‰ (2SD) in both procedures. With careful use of appropriate analytical conditions, the accuracy of SIMS analysis for δ34S approaches ± 0.3‰ (2SD) for chalcopyrite, pyrite and pyrrhotite and ± 0.6‰ for sphalerite. Measurements of δ34S in sub-20 µm grains of pyrite and sphalerite in ∼ 3.5 Ga cherts from the Pilbara craton, Western Australia show that this analytical technique is suitable for in situ sulfur isotope thermometry with ± 50 °C accuracy in appropriate samples, however, sulfides are not isotopically equilibrated in analyzed samples.

Chemical Geology↗

USGS2014

Mercury speciation in the Mt. Amiata mining district (Italy): interplay between urban activities and mercury contamination

A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl 2 , HgO and Hg 0 , were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

Tuscany↗

USGS2019

Reactivity of As and U co-occurring in mine wastes in northeastern Arizona

The reactivity of co-occurring arsenic (As) and uranium (U) in mine wastes was investigated using batch reactors, microscopy, spectroscopy, and aqueous chemistry. Analyses of field samples collected in proximity to mine wastes in northeastern Arizona confirm the presence of As and U in soils and surrounding waters, as reported in a previous study from our research group. In this study, we measured As (<0.500 to 7.77 μg/L) and U (0.950 to 165 μg/L) in waters, as well as mine wastes (<20.0 to 40.0 mg/kg As and <60.0 to 110 mg/kg U) and background solids (<20.0 mg/kg As and <60.0 mg/kg U). Analysis with X-ray fluorescence (XRF) and electron microprobe show the co-occurrence of As and U with iron (Fe) and vanadium (V). These field conditions served as a foundation for additional laboratory experiments to assess the reactivity of metals in these mine wastes. Results from laboratory experiments indicate that labile and exchangeable As(V) was released to solution when solids were sequentially reacted with water and magnesium chloride (MgCl 2 ), while limited U was released to solution with the same reactants. The predominance of As(V) in mine waste solids was confirmed by X-ray absorption near edge (XANES) analysis. Both As and U were released to solution after reaction of solids in batch experiments with HCO 3 − . Both X-ray photoelectron spectroscopy (XPS) and XANES analysis determined the predominance of Fe(III) in the solids. Mössbauer spectroscopy detected the presence of nano-crystalline goethite, Fe(II) and Fe(III) in (phyllo)silicates, and an unidentified mineral with parameters consistent with arsenopyrite or jarosite in the mine waste solids. Our results suggest that As and U can be released under environmentally relevant conditions in mine waste, which is applicable to risk and exposure assessment.

Arizona↗

USGS2004

Purification of triolein for use in semipermeable membrane devices (SPMDs)

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6×) partitioned against methanol. Tests of the procedure show that 14 C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 μg of methyl oleate as compared to sometimes more than 500 μg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.

Chemosphere↗

USGS2006

Assessment of pesticide residues in army cutworm moths (Euxoa auxiliaris) from the Greater Yellowstone Ecosystem and their potential consequences to foraging grizzly bears (Ursus arctos horribilis)

During summer, a grizzly bear ( Ursus arctos horribilis ) in the Greater Yellowstone Ecosystem (GYE) (USA) can excavate and consume millions of army cutworm moths ( Euxoa auxiliaris ) (ACMs) that aggregate in high elevation talus. Grizzly bears in the GYE were listed as threatened by the US Fish and Wildlife Service in 1975 and were proposed for delisting in 2005. However, questions remain about key bear foods. For example, ACMs are agricultural pests and concern exists about whether they contain pesticides that could be toxic to bears. Consequently, we investigated whether ACMs contain and transport pesticides to bear foraging sites and, if so, whether these levels could be toxic to bears. In 1999 we collected and analyzed ACMs from six bear foraging sites. ACMs were screened for 32 pesticides with gas chromatography with electron capture detection (GC–ECD). Because gas chromatography with tandem mass spectrometry (GC–MS/MS) can be more sensitive than GC–ECD for certain pesticides, we revisited one site in 2001 and analyzed these ACMs with GC–MS/MS. ACMs contained trace or undetectable levels of pesticides in 1999 and 2001, respectively. Based on chemical levels in ACMs and numbers of ACMs a bear can consume, we calculated the potential of chemicals to reach physiological toxicity. These calculations indicate bears do not consume physiologically toxic levels of pesticides and allay concerns they are at risk from pesticides transported by ACMs. If chemical control of ACMs changes in the future, screening new ACM samples taken from bear foraging sites may be warranted.

Wyoming↗

USGS2014

In vivo retention of ingested Au NPs by Daphnia magna: No evidence for trans-epithelial alimentary uptake

In vivo studies with Daphnia magna remain inconclusive as to whether engineered nanoparticles (NPs) are internalized into tissues after ingestion. Here we used a three-pronged approach to study the in vivo retention and efflux kinetics of 20 nm citrate stabilized Au NPs ingested by this key aquatic species. Daphnids were exposed to suspended particles (600 μg L −1 ) for 5 h after which they were depurated for 24 h in clean water containing algae. Light microscopy was used to follow the passage of Au NPs through the gastrointestinal tract, Au body burdens were determined by ICP-MS (inductively coupled plasma mass spectrometry), and transmission electron microscopy (TEM) was used to examine the presence and distribution of Au NPs in tissues. Results revealed that the elimination of Au NPs was bi-phasic. The fast elimination phase lasted <1 h and the rate constant at which Au (of Au NPs) was eliminated was 1.12 ± 0.34 h −1 (±SE) which accounted for ∼75% of the ingested Au. The remaining ∼25% of the ingested Au NPs was eliminated at a 100-fold slower rate. TEM analysis revealed that Au NPs in the midgut were in close proximity to the peritrophic membrane after 1 and 24 h of depuration. There were no observations of Au NP uptake at the microvilli. Thus, although Au NPs were retained in the gut lumen, there was no observable internalization into the gut epithelial cells. Similar to carbon nanotubes and CuO NPs, our findings indicate that in daphnids the in vivo retention of Au NPs does not necessarily result in their internalization.

Chemosphere↗

USGS2016

The effects of co-contaminants and native wetland sediments on the activity and dominant transformation mechanisms of a 1,1,2,2-tetrachloroethane (TeCA)-degrading enrichment culture

Bioremediation strategies, including bioaugmentation with chlorinated ethene-degrading enrichment cultures, have been successfully applied in the cleanup of subsurface environments contaminated with tetrachloroethene (PCE) and/or trichloroethene (TCE). However, these compounds are frequently found in the environment as components of mixtures that may also contain chlorinated ethanes and methanes. Under these conditions, the implementation of bioremediation may be complicated by inhibition effects, particularly when multiple dehalorespirers are present. We investigated the ability of the 1,1,2,2-tetrachloroethane (TeCA)-dechlorinating culture WBC-2 to biotransform TeCA alone, or a mixture of TeCA plus PCE and carbon tetrachloride (CT), in microcosms. The microcosms contained electron donors provided to biostimulate the added culture and sediment collected from a wetland where numerous “hotspots” of contamination with chlorinated solvent mixtures exist. The dominant TeCA biodegradation mechanism mediated by the WBC-2 culture in the microcosms was different in the presence of these wetland sediments than in the sediment-free enrichment culture or in previous WBC-2 bioaugmented microcosms and column tests conducted with wetland sediment collected at nearby sites. The co-contaminants and their daughter products also inhibited TeCA biodegradation by WBC-2. These results highlight the need to conduct biodegradability assays at new sites, particularly when multiple contaminants and dehalorespiring populations are present.

Chemosphere↗

USGS2008

Multi-residue method for the analysis of 85 current-use and legacy pesticides in bed and suspended sediments

A multi-residue method was developed for the simultaneous determination of 85 current-use and legacy organochlorine pesticides in a single sediment sample. After microwave-assisted extraction, clean-up of samples was optimized using gel permeation chromatography and either stacked carbon and alumina solid-phase extraction cartridges or a deactivated Florisil column. Analytes were determined by gas chromatography with ion-trap mass spectrometry and electron capture detection. Method detection limits ranged from 0.6 to 8.9 ??g/kg dry weight. Bed and suspended sediments from a variety of locations were analyzed to validate the method and 29 pesticides, including at least 1 from every class, were detected.

Journal of Chromatography A↗

USGS2004

Surface complexation model of uranyl sorption on Georgia kaolinite

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3–10), total U (1 and 10 μmol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uraniumwas preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO 2 , its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite.

Applied Clay Science↗

USGS2005

Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: Influence from siliceous and iron-rich calcic hydrothermal fluids

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, Rr =2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 ??C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed. The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 ??g/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 ??g/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 ??g/g Pd, 1.23 ??g/g Pt, and 0.05 ??g/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids. ?? 2004 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2006

Chemical evolution of Miocene wood: Example from the Belchatow brown coal deposit, central Poland

Miocene conifer wood samples from the Belchatow brown coal deposit in Poland were studied in order to discuss a range of chemical variations that occur as a result of biochemical coalification. Petrographic analysis, ultimate analysis, electron microprobe technique, and FTIR spectroscopy were used in this study. Our data show several progressive trends in functional groups distribution that take place during the wood transformation from group 1 to group 4, such as an overall increase in aromaticity, an increase in lignin/cellulose ratio, and an increase in oxygen functionalities. Other observations include an increase in aliphatic stretching and bending functionalities from groups 1 to 3; followed by a decrease in the wood of group 4; appearance of aliphatic out-of-plane bands in group 3 and increase in group 4; an increase in CH2/CH3 in group 4 compared to the other groups; and decrease in O-H groups in group 4 compared to other groups. These observations, together with other chemical and petrological observations, indicate that the progressive elimination of cellulose and modification of lignin are dominant processes of the wood transformation. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗