Aerobic oxidation of arsenite to arsenate by Cu(ii-chitosan/O[subscript 2] in Fenton-like reaction, a XANES investigation
Abstract not provided
Pincus, Lauren N.↗
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Hydrogen passivation of interstitial iron in boron-doped multicrystalline silicon during annealing
Effective hydrogenation of interstitial iron in boron-doped multicrystalline silicon wafers is reported. The multicrystalline silicon wafers were annealed with plasma-enhanced chemical vapour deposited silicon nitride films, at temperatures of 400 °C – 900 °C and for times from minutes to hours. At low temperatures where a combined effect of hydrogenation and precipitation of dissolved Fe is expected, results show that the hydrogenation process dominates the effect of precipitation. The concentrations of dissolved interstitial iron reduce by more than 90% after a 30-min anneal at temperatures between 600 and 900 °C. The most effective reduction occurs at 700 °C, where 99% of the initial dissolved iron is hydrogenated after 30 min. The results show that the observed reductions in interstitial Fe concentrations are not caused by the internal gettering of Fe at structural defects or by an enhanced diffusivity of Fe due to the presence of hydrogen. The hydrogenation process is conjectured to be the pairing of positively charged iron with negatively charged hydrogen, forming less recombination active Fe-H complexes in silicon.
36 MATERIALS SCIENCE↗
Investigating vibrational relaxation in cyanide-bridged transition metal mixed-valence complexes using two-dimensional infrared and infrared pump-probe spectroscopies
Using polarization-selective two-dimensional infrared (2D IR) and infrared pumpprobe spectroscopies, we study vibrational relaxation of the four cyanide stretching (CN) vibrations found in [(NH3)5RuIIINCFeII(CN)5] (FeRu) dissolved in D2O or formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5] 4 (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled CN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the CN modes are 2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the CN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on 1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans CN modes exhibit a 3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic CN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
[Cu(aq)] 2+ is structurally plastic and the axially elongated octahedron goes missing
High resolution (k = 18 Å –1 or k = 17 Å –1 ) copper K-edge EXAFS and MXAN (Minuit X-ray Absorption Near Edge) analyses have been used to investigate the structure of dissolved [Cu(aq)] 2+ in 1,3-propanediol (1,3-P) or 1,5-pentanediol (1,5-P) aqueous frozen glasses. EXAFS analysis invariably found a single axially asymmetric 6-coordinate (CN6) site, with 4×O eq = 1.97 Å, O ax1 = 2.22 Å, and O ax2 = 2.34 Å, plus a second-shell of 4×O water = 3.6 Å. However, MXAN analysis revealed that [Cu(aq)] 2+ occupies both square pyramidal (CN5) and axially asymmetric CN6 structures. The square pyramid included 4×H 2 O = 1.95 Å and 1×H 2 O = 2.23 Å. The CN6 sites included either a capped, near perfect, square pyramid with 5×H 2 O = 1.94 ± 0.04 Å and H 2 O ax = 2.22 Å (in 1,3-P) or a split axial configuration with 4×H 2 O = 1.94, H 2 O ax1 = 2.14 Å, and H 2 O ax2 = 2.28 Å (in 1,5-P). The CN6 sites also included an 8-H 2 O second-shell near 3.7 Å, which was undetectable about the strictly pyramidal sites. Equatorial angles averaging 94° ± 5° indicated significant departures from tetragonal planarity. MXAN assessment of the solution structure of [Cu(aq)] 2+ in 1,5-P prior to freezing revealed the same structures as previously found in aqueous 1M HClO 4 , which have become axially compressed in the frozen glasses. [Cu(aq)] 2+ in liquid and frozen solutions is dominated by a 5-coordinate square pyramid, but with split axial CN6 appearing in the frozen glasses. Among these phases, the Cu–O axial distances vary across 1 Å, and the equatorial angles depart significantly from the square plane. Although all these structures remove the d x 2 –y 2 , d z 2 degeneracy, no structure can be described as a Jahn-Teller (JT) axially elongated octahedron. The JT-octahedral description for dissolved [Cu(aq)] 2+ should thus be abandoned in favor of square pyramidal [Cu(H 2 O) 5 ] 2+ . The revised ligand environments have bearing on questions of the Cu(i)/Cu(ii) self-exchange rate and on the mechanism for ligand exchange with bulk water. In conclusion, the plasticity of dissolved Cu(ii) complex ions falsifies the foundational assumption of the rack-induced bonding theory of blue copper proteins and obviates any need for a thermodynamically implausible protein constraint.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Constraints on the magnitude and rate of CO2 dissolution at Bravo Dome natural gas field
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nuclear (including radiation effects), carbon sequ↗
Linked nitrogen and carbon dynamics reveal distinct pools and patterns in a deep, weathered bedrock rhizosphere
Nitrogen is one of the most limiting nutrients to forest productivity worldwide. Recently, it has been established that diverse ecosystems source a substantial fraction of their water from weathered bedrock, leading to questions about whether root-driven nitrogen cycling extends into weathered bedrock as well. In this study, we specifically examined nitrogen dynamics using specialized instrumentation distributed across a 16 m weathered bedrock vadose zone (WBVZ) underlying an old growth forest in northern California where the rhizosphere—composed of plant roots and their associated microbiome—extends meters into rock. We documented total dissolved nitrogen (TDN), dissolved organic carbon (DOC), inorganic nitrogen (ammonium and nitrate), and CO 2 and O 2 gases every 1.5 m to 16 m depth for 2 y. We found that TDN concentrations increased with depth, were an order of magnitude greater at 15 m than in the upper 30 cm, and that the majority of TDN throughout the weathered bedrock vadose zone was organic. We also found that TDN concentrations are influenced by depth, season, and interannual precipitation patterns. Carbon isotope composition of the DOC suggests that dissolved organic matter in the WBVZ is primarily derived from plant sources, and not the nitrogen-rich bedrock. We conclude that nitrogen dynamics in the WBVZ may be driven, in part, by an active rhizosphere, meters below the base of soil, and we argue that weathered bedrock horizons may play a key role in C-N cycling in ecosystems with deep-rooted plants.
Science & Technology - Other Topics↗
Chlorophyll- a dynamics in the lower Amazon River: insights from in situ and hyperspectral remote sensing using OCI-PACE
Chlorophyll-a concentration (Chla) is a key indicator of phytoplankton biomass and aquatic trophic status. However, satellite-derived Chla in sediment-rich waters, such as those found in the Lower Amazon River, remains challenging. The present study characterizes in situ Chla levels and their relationships with geographic, physical, and biogeochemical parameters in the Lower Amazon. Data collected between 2014 and 2017 across four hydrological seasons included measurements of Chla, remote sensing reflectance, and water quality parameters such as total suspended sediment, conductivity, water surface temperature, dissolved oxygen, pH, dissolved organic carbon and coloured dissolved organic matter. An empirical model was developed to estimate Chla using simulated hyperspectral bands from NASA’s PACE mission, achieving high performance (R 2 = 0.76; RMSE = 0.11 μg·L −1 ). Red bands proved particularly effective for Chla retrieval, while the addition of ultraviolet bands further enhanced model accuracy. The application of the developed model to satellite imagery yielded results consistent with in situ observations for the same hydrologic season. Seasonal variation and geographic location were major factors influencing Chla dynamics. This study provides a novel contribution to Chla estimation in optically complex, highly turbid waters and highlights the potential of the PACE mission to enhance global aquatic ecosystem monitoring. In conclusion, by offering freely available hyperspectral data with high radiometric resolution, PACE represents a significant advancement in the realm of remote sensing of aquatic environments.
Amazon River↗
ABIOTIC O{sub 2} LEVELS ON PLANETS AROUND F, G, K, AND M STARS: POSSIBLE FALSE POSITIVES FOR LIFE?
In the search for life on Earth-like planets around other stars, the first (and likely only) information will come from the spectroscopic characterization of the planet's atmosphere. Of the countless number of chemical species terrestrial life produces, only a few have the distinct spectral features and the necessary atmospheric abundance to be detectable. The easiest of these species to observe in Earth's atmosphere is O{sub 2} (and its photochemical byproduct, O{sub 3}). However, O{sub 2} can also be produced abiotically by photolysis of CO{sub 2}, followed by recombination of O atoms with each other. CO is produced in stoichiometric proportions. Whether O{sub 2} and CO can accumulate to appreciable concentrations depends on the ratio of far-ultraviolet (FUV) to near-ultraviolet (NUV) radiation coming from the planet's parent star and on what happens to these gases when they dissolve in a planet's oceans. Using a one-dimensional photochemical model, we demonstrate that O{sub 2} derived from CO{sub 2} photolysis should not accumulate to measurable concentrations on planets around F- and G-type stars. K-star, and especially M-star planets, however, may build up O{sub 2} because of the low NUV flux from their parent stars, in agreement with some previous studies. On such planets, a “false positive” for life is possible if recombination of dissolved CO and O{sub 2} in the oceans is slow and if other O{sub 2} sinks (e.g., reduced volcanic gases or dissolved ferrous iron) are small. O{sub 3}, on the other hand, could be detectable at UV wavelengths (λ < 300 nm) for a much broader range of boundary conditions and stellar types.
79 ASTRONOMY AND ASTROPHYSICS↗
Perfluorodecalin to enhance reactive species delivery in plasma-biomaterial interactions
Treatment of biological tissue by non-thermal atmospheric pressure plasmas in air can often cause beneficial biological outcomes, commonly by generation and delivery of reactive oxygen and nitrogen species (RONS). Biological plasma treatment is often mediated through plasma-liquid interactions, wherein plasma-generated RONS are dissolved into the liquid phase and subsequently initiate liquid-phase chemistry. In this paper we report observations on plasma-liquid interactions using a biologically inert perfluorocarbon solvent—perfluorodecalin (PFD)—that is known to be useful in other biomedical applications. The present paper concerns thin films of liquid PFD applied to porous and non-porous surfaces and subsequent plasma exposure of these films. With PFD application as a thin film prior to plasma exposure, we observe evidence of delayed, but ultimately enhanced RONS delivery to non-porous surfaces and through porous underlying surfaces. We demonstrate that PFD dissolves and retains relatively high concentrations of plasma-produced RONS, especially NO 2 . When the thin liquid film of PFD evaporates during plasma exposure, there appears to be a relatively rapid release of dissolved RONS, potentially aiding certain applications.
42 ENGINEERING↗
Enhancing Microbial Sulfate Reduction of Hydrocarbons in Groundwater Using Permeable Filled Borings
At a service station closed in 1993, groundwater contained benzene that persisted above the cleanup goal of 1 mg/L in zones depleted of background sulfate. The benzene and other petroleum hydrocarbons (PHCs) were present as much as 36 feet (11 m) below the water table and therefore remediation of a thick saturated zone interval was required. Microcosms using site sediments demonstrated that anaerobic benzene biodegradation occurred only if sulfate was added, suggesting sulfate addition as a remediation approach. Twenty-four boreholes (9.1" diameter and 56' deep) were drilled around four monitoring wells, in which benzene concentrations exceeded 1 mg/L. The boreholes were backfilled with a mixture of gravel and 15,000 pounds of gypsum (which releases sulfate as it dissolves) to create “Permeable Filled Borings” (PFBs). Concurrently, nine high pressure injections (HPIs) of gypsum slurry were conducted in other site locations (312 pounds of gypsum total). PFBs were expected to release sulfate for up to 20 years, whereas HPIs were expected to produce a short-lived plume of sulfate. Concentrations of benzene and sulfate in groundwater were monitored over a 3-year period in six monitoring wells. In two wells near PFBs, benzene concentrations dropped below the cleanup goal by two to three orders of magnitude; in one well, sulfate concentrations exceeded 500 mg/L for the most recent 18 months. Benzene concentrations in two other PFB monitoring wells declined by a factor of 2 to 4, but remained above 1 mg/L, presumably due to high-dissolved PHC concentrations and possibly greater residual PHC mass in adjacent sediments, and therefore greater sulfate demand. However, hydrogen and sulfur isotopic enrichment in benzene and sulfate, respectively, confirmed biodegradation of benzene and stimulation of sulfate-reducing conditions. Thus, it is hypothesized that the PHC mass in adjacent sediments will decline over time, as will dissolved PHC concentrations, and eventually benzene concentrations will decrease below the cleanup goal. Benzene in two HPI monitoring wells was below the cleanup goal for all but one sampling event before HPIs were conducted and remained below the cleanup goal after HPIs; there was no stimulation of sulfate-reducing conditions. It is concluded that sulfate released from PFBs contributed to declining benzene concentrations.
54 ENVIRONMENTAL SCIENCES↗
Formation of Hg(II) tetrathiolate complexes with cysteine at neutral pH
Mercury(II) ions precipitate from aqueous cysteine (H 2 Cys) solutions containing H 2 Cys/Hg(II) mole ratio ≥ 2.0 as Hg( S -HCys) 2 . In absence of additional cysteine, the precipitate dissolves at pH ~12 with the [Hg( S , N -Cys) 2 ] 2- complex dominating. With excess cysteine (H 2 Cys/Hg(II) mole ratio ≥ 4.0), higher complexes form and the precipitate dissolves at lower pH values. Previously, we found that tetrathiolate [Hg( S -Cys) 4 ] 6- complexes form at pH = 11.0; in this work we extend the investigation to pH values of physiological interest. We examined two series of Hg(II)-cysteine solutions in which C Hg(II) varied between 8 – 9 mM and 80 – 100 mM, respectively, with H 2 Cys/Hg(II) mole ratios from 4 to ~20. The solutions were prepared in the pH range 7.1 – 8.8, at the pH at which the initial Hg( S -HCys) 2 precipitate dissolved. The variations in the Hg(II) speciation were followed by 199 Hg NMR, X-ray absorption and Raman spectroscopic techniques. Our results show that in the dilute solutions (C Hg(II) = 8 – 9 mM), mixtures of di-, tri- (major) and tetrathiolate complexes exist at moderate cysteine excess (C H2Cys ~ 0.16 M) at pH 7.1. In the more concentrated solutions (C Hg(II) = 80 – 100 mM) with high cysteine excess (C H2Cys > 0.9 M), tetrathiolate [Hg( S -cysteinate) 4 ] m-6 ( m = 0 – 4) complexes dominate in the pH range 7.3 – 7.8, with lower charge than for the [Hg( S -Cys) 4 ] 6- complex due to protonation of some ( m ) of the amino groups of the coordinated cysteine ligands. In conclusion, the results of this investigation could provide a key to the mechanism of biosorption and accumulation of Hg(II) ions in biological / environmental systems.
199Hg NMR↗
Effect of Particle Size on the Dissolution of Pt 3 Co/C and Pt/C PEMFC Electrocatalysts
Potentiostatic and potentiodynamic Pt and Co dissolution were investigated for three Pt 3 Co/C catalysts with particle sizes of 4.9, 8.1, and 14.8 nm in aqueous electrolyte at potentials encountered by the PEMFC cathode. For all three Pt 3 Co/C catalysts under prolonged potentiostatic dissolution, the dissolved Pt steady state concentration increases from 0.85 V to reach a maximum at 1.1−1.15 V and decreases at higher potentials. The dependence of the dissolved Pt steady state concentration on particle size reveals that catalyst stability decreases with decreasing mean particle size, whereas the stability under potential cycling conditions is non-monotonic with particle size. Preferential dissolution of Co from all three Pt 3 Co catalysts was observed at all potentials, which increases at >1.1 V, the region over which Pt dissolution decreases, reflecting the opposing effects of Pt oxide formation on Pt and Co dissolution. Comparison of Pt 3 Co/C and Pt/C with similar mean particle sizes (4.9 vs 5.0 nm) and particle size distributions reveals that the Pt 3 Co/C has a higher potentiostatic dissolution rate (4–5 times), a higher steady state concentration of dissolved Pt (∼2 times), and a larger change in electrochemically-active surface area (ECA) (18 times) after prolonged cycling, indicating that Pt 3 Co has inferior stability. The higher rates of Pt dissolution for Pt 3 Co vs Pt have been attributed to higher extents of surface Pt oxidation, as determined using voltammetric oxide reduction charges and the white line intensities in Pt L 3 X-ray absorption spectra.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Membrane Degradation in PEM Fuel Cells: Part I. Modeling Gas Crossover and the Pt Band
Understanding chemical degradation of the proton-exchange membrane in fuel cells is crucial for extending their lifetimes. Herein, various degradation reactions reported in literature are organized and analyzed, including direct radical generation and an indirect (Fenton) pathway. To understand the transport of dissolved H 2 and O 2 crossover gases as they relate to membrane degradation, an agglomerate-scale model is introduced, treating gas, ionomer, and catalyst as discrete phases. The model reveals a key phenomenon: at working potentials, dissolved gases are mostly consumed at the interface between the catalyst layer and the membrane, leaving little gas to cross the membrane. Under open-circuit conditions, dissolved gases are not consumed and can then cross the membrane. This explains high H 2 O 2 concentrations and degradation rates seen in experiments but not captured in previous models. Following mixed-potential theory, crossover gases supply the hydrogen-oxidation and oxygen-reduction reactions, which occur simultaneously on individual Pt particles comprising the Pt band in the membrane, forming reactive species (H 2 O 2 , OH·). Results show crossover gas almost entirely reacts on the Pt band, allowing little to reach the opposite electrode. Furthermore, the micro-scale geometry of the catalyst-layer/membrane interface impacts the gas crossover at working potentials, indicating that cell construction affects membrane durability.
Johnson, Evan F. [Lawrence Berkeley National Labor↗
Evaluating ion exchange resin efficiency and oxidative capacity for the separation of uranium(IV) and uranium(VI)
Background: Previously described methods to separate dissolved U(IV) from dissolved U(VI) under acidic anoxic conditions prior to laboratory analysis were ineffective with materials currently available commercially. Three strong anion exchange resins were examined for their efficiency in separating, recovering, and preserving both redox states during separation. Results: Under oxic conditions, recovery of U(VI) from three exchange resins (Bio-Rad AG® 1x8 Poly-Prep® prefilled columns, Bio-Rad AGW 1x8 powder, and Dowex® 1x8 powder) ranged from 72% to 100% depending on the dosed mass, eluent volume, and resin selected. Dowex® 1x8 resin was the only resin found to provide 100% recovery of U (VI) with fewer than 5 bed volumes of eluent. Under anoxic conditions, all three resins oxidized U(IV) in aqueous solutions with relatively low U(IV) concentrations (<3x10-6 M). Resin-induced oxidation was observed visually using a leuco dye, safranin-o. Oxidants associated with the resin were irreversibly reduced by the addition of Ti(III). After anoxic resin pre-treatment, a series of U(IV)/U(VI) mixtures at micro-molar levels were prepared and separated using the Dowex® 1x8 resin with 100% recovery of both U(IV) and U(VI) with no resin-induced changes in oxidation state. Conclusions: Currently available anion exchange resins with apparently identical physical properties were found to have significantly different recoveries for hexavalent uranium at micro-molar concentrations. A novel qualitative technique was developed to visually assess oxidative capacities of anion exchange resins under acidic anoxic conditions. A protocol was developed for pre-treatment and use of currently available anion exchange resins to achieve quantitative separation of U(IV) and U(VI) in aqueous solutions with low U(IV) concentrations. This method can be applied to future work to quantitatively assess dissolved U(IV) and U(VI) concentrations in both laboratory and field samples.
54 ENVIRONMENTAL SCIENCES↗
A new model for the biodegradation kinetics of oil droplets: application to the Deepwater Horizon oil spill in the Gulf of Mexico
Oil biodegradation by native bacteria is one of the most important natural processes that can attenuate the environmental impacts of marine oil spills. Existing models for oil biodegradation kinetics are mostly for dissolved oil. This work developed a new mathematical model for the biodegradation of oil droplets and applied the model to estimate the time scale for oil biodegradation under conditions relevant to the Deepwater Horizon oil spill in the Gulf of Mexico. In the model, oil is composed of droplets of various sizes following the gamma function distribution. Each oil droplet shrinks during the microbe-mediated degradation at the oil-water interface. Using our developed model, we find that the degradation of oil droplets typically goes through two stages. The first stage is characterized by microbial activity unlimited by oil-water interface with higher biodegradation rates than that of the dissolved oil. The second stage is governed by the availability of the oil-water interface, which results in much slower rates than that of soluble oil. As a result, compared to that of the dissolved oil, the degradation of oil droplets typically starts faster and then quickly slows down, ultimately reaching a smaller percentage of degraded oil in longer time. The availability of the water-oil interface plays a key role in determining the rates and extent of degradation. We find that several parameters control biodegradation rates, including size distribution of oil droplets, initial microbial concentrations, initial oil concentration and composition. Under conditions relevant to the Deepwater Horizon spill, we find that the size distribution of oil droplets (mean and coefficient of variance) is the most important parameter because it determines the availability of the oil-water interface. Smaller oil droplets with larger variance leads to faster and larger extent of degradation. The developed model will be useful for evaluating transport and fate of spilled oil, different remediation strategies, and risk assessment.
02 PETROLEUM↗
[Data Set] East Fork Poplar Creek Sonde Data at Kilometer 5.4 Water Year 2012
This data set reports stream temperature, specific conductance, pH, dissolved oxygen percent saturation, dissolved oxygen concentration, turbidity, and fluorescent dissolved organic matter for East Fork Poplar Creek at a location approximately 5.4 kilometers upstream from the mouth of the creek.
East Fork Poplar Creek↗
[Data Set] East Fork Poplar Creek Sonde Data at Kilometer 5.4 Water Year 2013
This data set reports stream temperature, specific conductance, pH, dissolved oxygen percent saturation, dissolved oxygen concentration, turbidity, and fluorescent dissolved organic matter for East Fork Poplar Creek at a location approximately 5.4 kilometers
East Fork Poplar Creek↗
[Data Set] East Fork Poplar Creek Sonde Data at Kilometer 5.4 Water Year 2014
This data set reports stream temperature, specific conductance, pH, dissolved oxygen percent saturation, dissolved oxygen concentration, turbidity, and fluorescent dissolved organic matter for East Fork Poplar Creek at a location approximately 5.4 kilometers
East Fork Poplar Creek↗