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At least 433 records · Page 24Linked to original sources

USGS2018

International Society for Aeolian Research Distinguished Career Award, 2018 Joseph M. Prospero, Dr. Professor Emeritus, University of Miami

It is a pleasure and an honor to present Dr. Joseph M. Prospero of the University of Miami with the International Society for Aeolian Research(ISAR) Distinguished Career Award for 2018. Joe was born at home in Pottstown, Pennsylvania, one of three sons of Italian immigrant parents. He got interested in science, and particularly chemistry, not only out of curiosity, but also because of “...all the usual things. Color reactions...explosions....” Thus, his earliest experimental work was done with a Lionel Chem-Lab set in its classic chrome-yellow wooden box. Joe had parents who, despite their own lack of education,encouraged learning for Joe and his brothers through reading and education. He earned his B.S. in chemistry at Ursinus College in Collegeville, Pennsylvania in 1956. From there he went on to Princeton University for graduate school, studying radiochemistry and nuclear spectroscopy, receiving his M.A. in 1959 and his Ph.D. in 1963. On the encouragement of George Reynolds (a physicist at Princeton), Joe began his career at the Rosenstiel School of Marine and Atmospheric Science at the University of Miami in 1963. He has been studying dust everywhere on the planet–both on land and in the oceans–ever since.His research has been published in more than 170 papers and they are highly cited, showing the importance of dust in an astonishing diversity of the Earth’s natural systems, as well as its importance to human society.

Aeolian Research↗

USGS2011

Copper localization, elemental content, and thallus colour in the copper hyperaccumulator lichen Lecanora sierrae from California

An unusual dark blue-green lichen, Lecanora sierrae , was discovered over 30 years ago by Czehura near copper mines in the Lights Creek District, Plumas County, Northern California. Using atomic absorption spectroscopy, Czehura found that dark green lichen samples from Warren Canyon contained 4% Cu in ash and suggested that its colour was due to copper accumulation in the cortex. The present study addressed the hypothesis that the green colour in similar material we sampled from Warren Canyon in 2008, is caused by copper localization in the thallus. Optical microscopy and electron microprobe analysis of specimens of L. sierrae confirmed that copper localization took place in the cortex. Elemental analyses of L. sierrae and three other species from the same localities showed high enrichments of copper and selenium, suggesting that copper selenates or selenites might occur in these lichens and be responsible for the unusual colour.

Lichenologist↗

USGS2020

Nanoscale molecular composition of solid bitumen from the Eagle Ford Group across a natural thermal maturity gradient

Microscopic solid bitumen is a petrographically defined secondary organic matter residue produced during petroleum generation and subsequent oil transformation. The presence of solid bitumen impacts many reservoir properties including porosity, permeability, and hydrocarbon generation and storage, among others. Furthermore, solid bitumen reflectance is an important parameter for assessing the thermal maturity of formations with little to no vitrinite. While the molecular composition of solid bitumen will strongly impact associated parameters such as the development of organic matter porosity, hydrocarbon generation, and optical reflectance, assessing the molecular composition of solid bitumen in situ within shale reservoirs can be challenging due to the small grain sizes (often ≤1 μm in diameter) and the inherent heterogeneity of shale formations. Here we employ the recently developed atomic force microscopy based infrared spectroscopy (AFM-IR) technique to investigate solid bitumen molecular composition in situ within shale samples from the Late Cretaceous Eagle Ford Group. These samples possess sulfur-rich type II kerogens that span a natural thermal maturity gradient from early oil generation to the dry gas window. The application of AFM-IR allows for the rapid collection of thousands of compositional measurements from solid bitumen with ∼50 nm resolution. Our results indicate that (i) solid bitumen from the lower Eagle Ford displays both intra- and intergranular variation in the relative abundance of CH 2 , C═C, and C═O moieties present; (ii) this molecular variation tends to, but does not always, decrease with an increase in thermal maturity; and (iii) the solid bitumen composition between samples, from an atomic ratio perspective, is more similar than analysis of bulk kerogen isolates would indicate. These findings are discussed with perspective toward understanding the impact of thermal stress on the composition of secondary organic matter within the Eagle Ford Shale and highlight the growing awareness that organic matter heterogeneity within petroliferous mudrocks extends down to the nanoscale regime.

Energy and Fuels↗

USGS2021

Organo-facies and mineral effects on sorption capacity of low-maturity Permian Barakar shales from the Auranga Basin, Jharkhand, India

Shales associated with the Lower Permian (Barakar Formation) sediments of the Auranga Coalfield, India, occur in the immature–early mature stage. The sorption capacity of Barakar shale samples has been studied through high-pressure methane (CH 4 ) adsorption and low-pressure N 2 gas adsorption (LPN 2 GA) methods, supported with proximate analyses, programmed pyrolysis, optical petrography, and with energy-dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma mass spectrometry. The sorption capacity is a function of the organic and inorganic constituents present in the shale samples. The methane sorption capacity (MSC) and Langmuir volume of the shale samples vary from 0.217 to 0.314 and 0.315 to 0.429 mmol/g rock, respectively. The BET-calculated surface area of the studied shales varies from 8.12 to 30.36 m 2 /g. The sorption capacities show the importance of the total organic content (TOC) through weak but positive correlations with MSC ( r 2 = 0.45) and S 1 values (mg hydrocarbons/g rock from programmed pyrolysis; r 2 = 0.40). Moreover, apparent inverse relationships were observed between MSC and clay mineral abundances, suggesting that individual clay mineral types may influence MSC, although more work is needed. The TOC-normalized MSC (MSC*) of shale samples shows a positive trend with quartz plus clay mineral content and ash yield of r 2 = 0.64 for both. In addition, MSC* shows a negative logarithmic relationship with S 1 + S 2 ( r 2 = 0.63) and a positive linear relationship with TOC-normalized total organic matter (TOM*) ( r 2 = 0.88, when 5 low TOM* samples are excluded) indicating complex relationships possibly including bitumen retention in the sample pore spaces. The micropore study of the samples through LPN 2 GA, applying Dubinin–Radushkevich, Dubinin–Astakhov, and density functional theory models, shows the dominance of micro-mesopore concentrations in the shale matrix of ∼2 nm pore diameter. However, these pores might be present as blind or closed pores. The presence of thorium and zirconium is reflective of terrigenous detrital matter, i.e., moderately to strongly recycled sediments. The fluviatile facies of deposited shales in the Auranga Coalfield are noted by the significant presence of kaolinite (32.5–78.3%), which suggests the importance of its effect on the sorption capacity of proximal terrigenous shales.

Jharkhand↗

USGS2015

Detailed description of oil shale organic and mineralogical heterogeneity via fourier transform infrared mircoscopy

Mineralogical and geochemical information on reservoir and source rocks is necessary to assess and produce from petroleum systems. The standard methods in the petroleum industry for obtaining these properties are bulk measurements on homogenized, generally crushed, and pulverized rock samples and can take from hours to days to perform. New methods using Fourier transform infrared (FTIR) spectroscopy have been developed to more rapidly obtain information on mineralogy and geochemistry. However, these methods are also typically performed on bulk, homogenized samples. We present a new approach to rock sample characterization incorporating multivariate analysis and FTIR microscopy to provide non-destructive, spatially resolved mineralogy and geochemistry on whole rock samples. We are able to predict bulk mineralogy and organic carbon content within the same margin of error as standard characterization techniques, including X-ray diffraction (XRD) and total organic carbon (TOC) analysis. Validation of the method was performed using two oil shale samples from the Green River Formation in the Piceance Basin with differing sedimentary structures. One sample represents laminated Green River oil shales, and the other is representative of oil shale breccia. The FTIR microscopy results on the oil shales agree with XRD and LECO TOC data from the homogenized samples but also give additional detail regarding sample heterogeneity by providing information on the distribution of mineral phases and organic content. While measurements for this study were performed on oil shales, the method could also be applied to other geological samples, such as other mudrocks, complex carbonates, and soils.

Energy & Fuels↗

USGS2026

Oil in the Alaska North Slope gas hydrate reservoir: Micro-CT and flow simulation insights into permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 300 3 -voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

Alaska↗

USGS2016

Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

Energy & Fuels↗

USGS2019

Experimental study on the impact of thermal maturity on shale microstructures using hydrous pyrolysis

Hydrous pyrolysis was applied to four low-maturity aliquots from the Utica, Excello, Monterey, and Niobrara Shale Formations in North America to create artificial maturation sequences, which could be used to study the impact of maturation on geochemical and microstructural properties. Modified Rock-Eval pyrolysis, reflectance, organic petrology, and Fourier transform infrared spectroscopy (FTIR) were employed to analyze their geochemical properties, while gas adsorption (CO 2 and N 2 ) was used to characterize their pore structures (pores < 200 nm). Organic petrography using white and blue light (fluorescence) before and after hydrous pyrolysis showed that amorphous organic matter cracked into solid bitumen, oil, and gas during hydrous pyrolysis. A reduction of the CH 2 /CH 3 ratio in hydrous pyrolysis residues was observed from FTIR analysis. Rock-Eval pyrolysis showed that kerogens in the four samples were dissimilar, and hydrous pyrolysis residues showed smaller hydrogen index and Sh2 values than starting materials. Results from CO 2 and N 2 gas adsorption analysis showed that pore structures (micropore volume, micropore surface area, meso-macropore volume, and meso-macropore surface area) changed significantly during hydrous pyrolysis. However, changes in pore structure were dissimilar among the four samples, which was attributed to different activation energies of organic matter. A thermodynamic fractal model showed a decrease in fractal dimensions of Utica, Monterey, and Excello after hydrous pyrolysis, indicating a decrease in surface roughness. The pore size heterogeneity in the Utica sample increased as hydrous pyrolysis temperature increased, whereas the pore size heterogeneity distributions in the Monterey and Excello decreased based on the N 2 adsorption data.

Energy & Fuels↗

USGS2019

Nanoscale molecular fractionation of organic matter within unconventional petroleum source beds

Fractionation of petroleum during migration through sedimentary rock matrices has been observed across lengths of meters to kilometers. Selective adsorption of specific chemical moieties at mineral surfaces and/or the phase behavior of petroleum during pressure changes typically are invoked to explain this behavior. Such phenomena are of interest as they impact both the quality and recoverability of petroleum resources. Given the current emphasis on unconventional (continuous) resources, there is a need to understand petroleum fractionation occurring during expulsion and migration at the nanometer to micron scale, due to the fine-grained nature of petroliferous mudrocks. Here, organic matter compositional differences observed within kukersites (petroleum source beds containing acritarch Gloeocapsomorpha prisca) and the overlying carbonate reservoir layer from the Ordovician Stonewall Formation are explored using a suite of spectroscopic methods, primarily through atomic force microscopy based infrared spectroscopy (AFM-IR). AFM-IR is capable of providing spatial resolutions approaching 50 nm and allows for assessment of the molecular fingerprint of kukersite organic matter across transition zones from organic-rich ‘source’ layers into neighboring carbonate ‘reservoir’ layers ~150 μm away. Results indicate that organic matter composition begins to vary immediately following expulsion from source layers, with loss of carbonyl groups and a concomitant decrease in alkyl chain-length, as migration distance increases. These chemical transitions correlate with a decrease in fluorescence intensity, increase in solid bitumen reflectance, and increase in Raman aromaticity proxies (D-G band separation) in the organic matter. Our findings are consistent with the retention of polar compounds onto mineral grains during expulsion and migration, following primary cracking and bituminization of the Gloeocapsomorpha prisca kerogen.

Energy and Fuels↗

USGS2021

Demethylation of methylmercury in bird, fish, and earthworm

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate (Hg(Sec)4) complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy and chromatography-ICP mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms, and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.

Environmental Science & Technology↗

USGS2015

Anaerobic chemolithotrophic growth of the haloalkaliphilic bacterium strain MLMS‑1 by disproportionation of monothioarsenate

A novel chemolithotrophic metabolism based on a mixed arsenic−sulfur species has been discovered for the anaerobic deltaproteobacterium, strain MLMS-1, a haloalkaliphile isolated from Mono Lake, California, U.S. Strain MLMS‑1 is the first reported obligate arsenate-respiring chemoautotroph which grows by coupling arsenate reduction to arsenite with the oxidation of sulfide to sulfate. In that pathway the formation of a mixed arsenic−sulfur species was reported. That species was assumed to be monothioarsenite ([H2AsIIIS−IIO2] −), formed as an intermediate by abiotic reaction of arsenite with sulfide. We now report that this species is monothioarsenate ([HAsVS−IIO3] 2−) as revealed by X-ray absorption spectroscopy. Monothioarsenate forms by abiotic reaction of arsenite with zerovalent sulfur. Monothioarsenate is kinetically stable under a wide range of pH and redox conditions. However, it was metabolized rapidly by strain MLMS-1 when incubated with arsenate. Incubations using monothioarsenate confirmed that strain MLMS-1 was able to grow (μ = 0.017 h−1 ) on this substrate via a disproportionation reaction by oxidizing the thio-group-sulfur (S−II) to zerovalent sulfur or sulfate while concurrently reducing the central arsenic atom (AsV) to arsenite. Monothioarsenate disproportionation could be widespread in nature beyond the already studied arsenic and sulfide rich hot springs and soda lakes where it was discovered.

Environmental Science & Technology↗

USGS2025

Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques

The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.

Environmental Science and Technology↗

USGS2026

Widespread occurrence of Magnéli phases in wildland-urban interface fire ashes

The increasing activity of wildland–urban interface (WUI) fires has raised concerns regarding the potential environmental and human health impacts of residual ash remaining after burning. In this study, we investigated the concentration and speciation of titanium in WUI fire ash. Total titanium concentrations in WUI fire ash ranged from 0.53 to 80 g kg –1 . Synchrotron-based macro- and microscale X-ray absorption near-edge structure (XANES and μXANES, respectively) spectroscopy were used to quantify the relative abundance of major Ti phases in the fire ash, and the results were corroborated by high resolution-transmission electron microscopy (HR-TEM) measurements. Rutile (α-TiO 2 ), anatase (β-TiO 2 ), ilmenite (FeTiO 3 ), and titanium(III) oxide (Ti 2 O 3 ) were detected in all 20 ashes investigated by XANES and accounted for 0.26–0.83, 0.19–0.83, 0.33, and 0.17–0.72 of the spectral weight, respectively. Deeper analysis by μXANES of one sample demonstrated that Ti-bearing particles occurred as a mixture of rutile (α-TiO 2 ), anatase (β-TiO 2 ), ilmenite (FeTiO 3 ), and titanium(III) oxide Ti 2 O 3, with the absence of a pure Ti 2 O 3 phase. The presence of Ti 2 O 3 in the WUI fire ash is ascribed to the reduction of rutile and anatase to Magnéli titania (Ti n O 2 n– 1 , n = 4–9), which is estimated to be the dominant phase of titanium in the 20 WUI fire ashes investigated by XANES. The occurrence of Magnéli titania was corroborated by HR-TEM. Our findings demonstrate the impact of WUI fires on titanium speciation; fires convert titanium dioxides (e.g., rutile and anatase) to reduced titanium phases (e.g., Magnéli titania). Based on HR-TEM analyses, most of the titanium-bearing particles were less than 500 nm in size. Magnéli particles have been shown to be more toxic than rutile and anatase and have been linked to reduced lung function. Therefore, this study provides critical insights into the pollution characteristics and potential health risks of WUI fire ashes and associated particles, which are currently poorly understood.

California↗

USGS2017

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida↗

USGS2017

Modifications to EPA Method 3060A to Improve Extraction of Cr(VI) from Chromium Ore Processing Residue-Contaminated Soils

It has been shown that EPA Method 3060A does not adequately extract Cr(VI) from chromium ore processing residue (COPR). We modified various parameters of EPA 3060A toward understanding the transformation of COPR minerals in the alkaline extraction and improving extraction of Cr(VI) from NIST SRM 2701, a standard COPR-contaminated soil. Aluminum and Si were the major elements dissolved from NIST 2701, and their concentrations in solution were correlated with Cr(VI). The extraction fluid leached additional Al and Si from the method-prescribed borosilicate glass vessels which appeared to suppress the release of Cr(VI). Use of polytetrafluoroethylene vessels and intensive grinding of NIST 2701 increased the amount of Cr(VI) extracted. These modifications, combined with an increased extraction fluid to sample ratio of ≥900 mL g –1 and 48-h extraction time resulted in a maximum release of 1274 ± 7 mg kg –1 Cr(VI). This is greater than the NIST 2701 certified value of 551 ± 35 mg kg –1 but less than 3050 mg kg –1 Cr(VI) previously estimated by X-ray absorption near edge structure spectroscopy. Some of the increased Cr(VI) may have resulted from oxidation of Cr(III) released from brownmillerite which rapidly transformed during the extractions. Layered-double hydroxides remained stable during extractions and represent a potential residence for unextracted Cr(VI).

Environmental Science & Technology↗

USGS2017

Effects of sulfide concentration and dissolved organic matter characteristics on the structure of nanocolloidal metacinnabar

Understanding the speciation of divalent mercury (Hg(II)) in aquatic systems containing dissolved organic matter (DOM) and sulfide is necessary to predict the conversion of Hg(II) to bioavailable methylmercury. We used X-ray absorption spectroscopy to characterize the structural order of mercury in Hg(II)–DOM–sulfide systems for a range of sulfide concentration (1–100 μM), DOM aromaticity (specific ultraviolet absorbance (SUVA 254 )), and Hg(II)–DOM and Hg(II)–DOM–sulfide equilibration times (4–142 h). In all systems, Hg(II) was present as structurally disordered nanocolloidal metacinnabar (β-HgS). β-HgS nanocolloids were significantly smaller or less ordered at lower sulfide concentration, as indicated by under-coordination of Hg(II) in β-HgS. The size or structural order of β-HgS nanocolloids increased with increasing sulfide abundance and decreased with increasing SUVA 254 of the DOM. The Hg(II)–DOM or Hg(II)–DOM–sulfide equilibration times did not significantly influence the extent of structural order in nanocolloidal β-HgS. Geochemical factors that control the structural order of nanocolloidal β-HgS, which are expected to influence nanocolloid surface reactivity and solubility, should be considered in the context of mercury bioavailability.

Environmental Science & Technology↗

USGS2018

Phosphorus speciation and solubility in aeolian dust deposited in the interior American West

Aeolian dust is a significant source of phosphorus (P) to alpine oligotrophic lakes, but P speciation in dust and source sediments and its release kinetics to lake water remain unknown. Phosphorus K-edge XANES spectroscopy shows that calcium-bound P (Ca−P) is dominant in 10 of 12 dust samples (41−74%) deposited on snow in the central Rocky Mountains and all 42 source sediment samples (the fine fraction) (68−80%), with a lower proportion in dust probably because acidic snowmelt dissolves some Ca−P in dust before collection. Iron-bound P (Fe−P, ∼54%) dominates in the remaining two dust samples. Chemical extractions (SEDEX) on these samples provide inaccurate results because of unselective extraction of targeted species and artifacts introduced by the extractions. Dust releases increasingly more P in synthetic lake water within 6−72 h thanks to dissolution of Ca−P, but dust release of P declines afterward due to back adsorption of P onto Fe oxides present in the dust. The back sorption is stronger for the dust with a lower degree of P saturation determined by oxalate extraction. This work suggests that P speciation, poorly crystalline minerals in the dust, and lake acidification all affect the availability and fate of dust-borne P in lakes.

Arizona, Colorado, New Mexico, Utah↗

USGS2018

Effect of calcium on the bioavailability of dissolved uranium(VI) in plant roots under circumneutral pH

We integrated field measurements, hydroponic experiments, microscopy, and spectroscopy to investigate the effect of Ca(II) on dissolved U(VI) uptake by plants in 1 mM HCO 3 – solutions at circumneutral pH. The accumulation of U in plants (3.1–21.3 mg kg –1 ) from the stream bank of the Rio Paguate, Jackpile Mine, New Mexico served as a motivation for this study. Brassica juncea was the model plant used for the laboratory experiments conducted over a range of U (30–700 μg L –1 ) and Ca (0–240 mg L –1 ) concentrations. The initial U uptake followed pseudo-second-order kinetics. The initial U uptake rate ( V 0 ) ranged from 4.4 to 62 μg g –1 h –1 in experiments with no added Ca and from 0.73 to 2.07 μg g –1 h –1 in experiments with 12 mg L –1 Ca. No measurable U uptake over time was detected for experiments with 240 mg L –1 Ca. Ternary Ca–U–CO 3 complexes may affect the decrease in U bioavailability observed in this study. Elemental X-ray mapping using scanning transmission electron microscopy–energy-dispersive spectrometry detected U–P-bearing precipitates within root cell walls in water free of Ca. These results suggest that root interactions with Ca and carbonate in solution affect the bioavailability of U in plants. This study contributes relevant information to applications related to U transport and remediation of contaminated sites.

Environmental Science & Technology↗