CRYOGENIC TRAPPING OF OXIDIZED MERCURY SPECIES FROM COMBUSTION FLUE GAS. (R827649)

EPA Science Inventory

To further understand the speciation and partitioning of mercury species in combustion systems, it is necessary to be able to identify and quantitate the various forms of oxidized mercury. Currently accepted methods for speciating mercury (Ontario Hydro Method, EPA Method 29, ...

Citric-acid preacidification enhanced electrokinetic remediation for removal of chromium from chromium-residue-contaminated soil.

PubMed

Meng, Fansheng; Xue, Hao; Wang, Yeyao; Zheng, Binghui; Wang, Juling

2018-02-01

Electrokinetic experiments were conducted on chromium-residue-contaminated soils collected from a chemical plant in China. Acidification-electrokinetic remediation technology was proposed in order to solve the problem of removing inefficient with ordinary electrokinetic. The results showed that electrokinetic remediation removal efficiency of chromium from chromium-contaminated soil was significantly enhanced with acidizing pretreatment. The total chromium [Cr(T)] and hexavalent chromium [Cr(VI)] removal rate of the group acidized by citric acid (0.9 mol/L) for 5 days was increased from 6.23% and 19.01% in the acid-free experiments to 26.97% and 77.66% in the acidification-treated experiments, respectively. In addition, part of chromium with the state of carbonate-combined will be converted into water-soluble state through acidification to improve the removal efficiency. Within the appropriate concentration range, the higher concentration of acid was, the more chromium was released. So the removal efficiency of chromium depended on the acid concentration. The citric acid is also a kind of complexing agent, which produced complexation with Cr that was released by the electrokinetic treatment and then enhanced the removal efficiency. The major speciation of chromium that was removed from soils by acidification-electrokinetics remediation was acid-soluble speciation, revivification speciation and oxidation speciation, which reduced biological availability of chromium.

Iron solubility driven by speciation in dust sources to the ocean

USGS Publications Warehouse

Schroth, A.W.; Crusius, John; Sholkovitz, E.R.; Bostick, B.C.

2009-01-01

Although abundant in the Earths crust, iron is present at trace concentrations in sea water and is a limiting nutrient for phytoplankton in approximately 40% of the ocean. Current literature suggests that aerosols are the primary external source of iron to offshore waters, yet controls on iron aerosol solubility remain unclear. Here we demonstrate that iron speciation (oxidation state and bonding environment) drives iron solubility in arid region soils, glacial weathering products (flour) and oil combustion products (oil fly ash). Iron speciation varies by aerosol source, with soils in arid regions dominated by ferric (oxy)hydroxides, glacial flour by primary and secondary ferrous silicates and oil fly ash by ferric sulphate salts. Variation in iron speciation produces systematic differences in iron solubility: less than 1% of the iron in arid soils was soluble, compared with 2-3% in glacial products and 77-81% in oil combustion products, which is directly linked to fractions of more soluble phases. We conclude that spatial and temporal variations in aerosol iron speciation, driven by the distribution of deserts, glaciers and fossil-fuel combustion, could have a pronounced effect on aerosol iron solubility and therefore on biological productivity and the carbon cycle in the ocean. ?? 2009 Macmillan Publishers Limited.

Changes in zinc speciation with mine tailings acidification in a semi-arid weathering environment

PubMed Central

Hayes, Sarah M.; O’Day, Peggy A.; Webb, Sam M.; Maier, Raina M.; Chorover, Jon

2011-01-01

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semi-arid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6,000 to 450 mg kg−1) and plant-available (590 to 75 mg kg−1) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and micro-focused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn0.8talc), Zn sorbed to ferrihydrite (ZnadsFeOx), and zinc sulfate (ZnSO4·7H2O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly-crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Micro-scale analyses identified hetaerolite (ZnMn2O4), hemimorphite (Zn4Si2O7(OH)2·H2O) and sphalerite (ZnS) as minor phases. Bulk and micro-focused spectroscopy complement the chemical extraction results and highlight the importance of using a multi-method approach to interrogate complex tailings systems. PMID:21761897

Changes in zinc speciation with mine tailings acidification in a semiarid weathering environment.

PubMed

Hayes, Sarah M; O'Day, Peggy A; Webb, Sam M; Maier, Raina M; Chorover, Jon

2011-09-01

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.

A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

EPA Science Inventory

Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCann, Kevin; Sinkov, Sergey I.; Lumetta, Gregg J.

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV)more » to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.« less

Sulfur and iron speciation in gas-rich impact-melt glasses from basaltic shergottites determined by microXANES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, S.R.; Rao, M.N.; Nyquist, L.E.

2008-04-28

Sulfur and iron K XANES measurements were made on GRIM glasses from EET 79001. Iron is in the ferrous state. Sulfur speciation is predominately sulfide coordination but is Fe coordinated in Lith B and, most likely, Ca coordinated in Lith A. Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Moessbauer studies on rocks at Meridian and Gusev, whereas MgSO{sub 4} is deduced from MgO-SO{sub 3} correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum andmore » alunogen/S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. On Earth, volcanic rocks contain measurable quantities of sulfur present as both sulfide and sulfate. Carroll and Rutherford showed that oxidized forms of sulfur may comprise a significant fraction of total dissolved sulfur, if the oxidation state is higher than {approx}2 log fO{sub 2} units relative to the QFM buffer. Terrestrial samples containing sulfates up to {approx}25% in fresh basalts from the Galapagos Rift on one hand and high sulfide contents present in oceanic basalts on the other indicate that the relative abundance of sulfide and sulfate varies depending on the oxygen fugacity of the system. Basaltic shergottites (bulk) such as Shergotty, EET79001 and Zagami usually contain small amounts of sulfur ({approx}0.5%) as pyrrhotite. But, in isolated glass pockets containing secondary salts (known as GRIM glasses) in these meteorites, sulfur is present in high abundance ({approx}1-12%). To determine sulfur speciation (sulfide, sulfate or elemental sulfur) in these glasses, Gooding et al. and Burgess et al. carried out vacuum pyrolysis experiments on these GRIM glasses (also called Lith C) using quadrupole mass-spectrometric methods. They found that the evolved S-bearing gases from these samples consisted of both SO{sub 2} (from sulfate) and H{sub 2}S (from sulfide) in varying proportions. However, as mass-spectrometric studies do not provide details about spatial association of these S-species in these samples, we have studied the spatial distribution of sulfides and sulfates in GRIM glasses using sulfur K micro-XANES techniques in the present study. The microscale speciation of S may have important implications for the Rb-Sr isotope systematics of EET79001 Lith C glasses. In reference to oxidative weathering of surface basalts on Mars yielding secondary iron sulfates, Solberg and Burns examined a GRIM glass in EET79001 by Moessbauer spectroscopic techniques and showed that the percentage of Fe{sup 3+} in Lith C is <2%. They suggested that the Lith C contains very little Fe{sup 3+} despite the occurrence of oxidized sulfate in them, indicating that the conditions leading to the formation of these glasses were insufficiently oxidizing to produce Fe{sup 3+} from Fe{sup 2+} in these glasses. To understand the implications of these observations for the formation of the GRIM glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques. The S and Fe K micro-XANES measurements were performed on thin sections from EET79001: 506 from Lith A and 507 from Lith B.« less

SPECIATION ANALYSIS OF ARSENIC IN BIOLOGICAL MATRICES BY AUTOMATED HYDRIDE GENERATION-CRYOTRAPPING-ATOMIC ABSORPTION SPECTROMETRY WITH MULTIPLE MICROFLAME QUARTZ TUBE ATOMIZER (MULTIATOMIZER)

EPA Science Inventory

Abstract Analyses of arsenic (As) species in tissues and body fluids of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. We have previously described an oxidation state-specifi...

Measured solubilities and speciations from oversaturation experiments of neptunium, plutonium, and americium in UE-25p No. 1 well water from the Yucca Mountain region: Milestone report 3329-WBS1.2.3.4.1.3.1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nitsche, H.; Roberts, K.; Prussin, T.

1994-04-01

Solubility and speciation are important in understanding aqueous radionuclide transport through the geosphere. They define the source term for transport retardation processes such as sorption and colloid formation. Solubility and speciation data are useful in verifying the validity of geochemical codes that are a part of predictive transport models. Results are presented from solubility and speciation experiments of {sup 237}NpO{sub 2}{sup +}, {sup 239}Pu{sup 4+}, and {sup 241}Am{sup 3+}/Nd{sup 3+} in a modified UE-25p No. 1 groundwater (from the Yucca Mountain region, Nevada, which is being investigated as a potential high-level nuclear waste disposal site) at two different temperatures (25{degree}more » and 60{degree}C) and three pH values (6.0, 7.0, 8.5). The solubility-controlling steady-state solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined. The neptunium solubility decreased with increasing temperature and pH. Plutonium concentrations significantly decreased with increasing temperature at pH 6 and 7. The concentration at pH 8.5 hardly decreased at all with increasing temperature. At both temperatures the concentrations were highest at pH 8.5, lowest at pH 7, and in between at pH 6. For the americium/neodymium solutions, the solubility decreased significantly with increasing temperature and increased somewhat with increasing pH.« less

SORPTION OF ARSENATE AND ARSENITE ON RUO2 X H2O: ANALYSIS OF SORBED PHASE OXIDATION STATE BY XANES IN ADVANCED PHOTON SOURCE ACTIVITY REPORT 2002

EPA Science Inventory

The sorption reactions of arsenate (As(V)) and arsenite (As(III)) on RuO₂ x H₂O were examined by X-ray Absorption Near Edge Spectroscopy (XANES) to elucidate the solid state speciation of sorbed As. At all pH values studied (pH 4-8), RuO₂ x H

Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, B.D.; Amos, R.T.; Nico, P.S.

2010-03-15

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate themore » impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.« less

Oxidation State Specific Generation of Arsines from Methylated Arsenicals Based on L- Cysteine Treatment in Buffered Media for Speciation Analysis by Hydride Generation - Automated Cryotrapping - Gas Chromatography-Atomic Absorption Spectrometry with the Multiatomizer

PubMed Central

Matoušek, Tomáš; Hernández-Zavala, Araceli; Svoboda, Milan; Langrová, Lenka; Adair, Blakely M.; Drobná, Zuzana; Thomas, David J.; Stýblo, Miroslav; Dědina, Jiří

2008-01-01

An automated system for hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l−1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of L-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the L-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. PMID:18521190

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

PubMed

Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

2016-06-01

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of mercury speciation and removal through air pollution control devices of a 190 MW boiler.

PubMed

Wu, Chengli; Cao, Yan; Dong, Zhongbing; Cheng, Chinmin; Li, Hanxu; Pan, Weiping

2010-01-01

Air pollution control devices (APCDs) are installed at coal-fired power plants for air pollutant regulation. Selective catalytic reduction (SCR) and wet flue gas desulfurization (FGD) systems have the co-benefits of air pollutant and mercury removal. Configuration and operational conditions of APCDs and mercury speciation affect mercury removal efficiently at coal-fired utilities. The Ontario Hydro Method (OHM) recommended by the U.S. Environmental Protection Agency (EPA) was used to determine mercury speciation simultaneously at five sampling locations through SCR-ESP-FGD at a 190 MW unit. Chlorine in coal had been suggested as a factor affecting the mercury speciation in flue gas; and low-chlorine coal was purported to produce less oxidized mercury (Hg2+) and more elemental mercury (Hg0) at the SCR inlet compared to higher chlorine coal. SCR could oxidize elemental mercury into oxidized mercury when SCR was in service, and oxidation efficiency reached 71.0%. Therefore, oxidized mercury removal efficiency was enhanced through a wet FGD system. In the non-ozone season, about 89.5%-96.8% of oxidized mercury was controlled, but only 54.9%-68.8% of the total mercury was captured through wet FGD. Oxidized mercury removal efficiency was 95.9%-98.0%, and there was a big difference in the total mercury removal efficiencies from 78.0% to 90.2% in the ozone season. Mercury mass balance was evaluated to validate reliability of OHM testing data, and the ratio of mercury input in the coal to mercury output at the stack was from 0.84 to 1.08.

Macro- and microscale investigation of selenium speciation in Blackfoot river, Idaho sediments.

PubMed

Oram, Libbie L; Strawn, Daniel G; Marcus, Matthew A; Fakra, Sirine C; Möller, Gregory

2008-09-15

The transport and bioavailability of selenium in the environment is controlled by its chemical speciation. However, knowledge of the biogeochemistry and speciation of Se in streambed sediment is limited. We investigated the speciation of Se in sediment cores from the Blackfoot River (BFR), Idaho using sequential extractions and synchrotron-based micro-X-ray fluorescence (micro-SXRF). We collected micro-SXRF oxidation state maps of Se in sediments, which had not been done on natural sediment samples. Selective extractions showed that most Se in the sediments is present as either (1) nonextractable Se or (2) base extractable Se. Results from micro-SXRF showed three defined species of Se were present in all four samples: Se(-II,O), Se(IV), and Se(VI). Se(-II,O) was the predominant species in samples from one location, and Se(IV) was the predominant species in samples from a second location. Results from both techniques were consistent, and suggested that the predominant species were Se(-II) species associated with recalcitrant organic matter, and Se(IV) species tightly bound to organic materials. This information can be used to predict the biogeochemical cycling and bioavailability of Se in streambed sediment environments.

Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

PubMed

Ikeda-Ohno, Atsushi; Harrison, Jennifer J; Thiruvoth, Sangeeth; Wilsher, Kerry; Wong, Henri K Y; Johansen, Mathew P; Waite, T David; Payne, Timothy E

2014-09-02

During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed.

Effects of iron on arsenic speciation and redox chemistry in acid mine water

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2005-01-01

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Chemically and geographically distinct solid-phase iron pools in the Southern Ocean.

PubMed

von der Heyden, B P; Roychoudhury, A N; Mtshali, T N; Tyliszczak, T; Myneni, S C B

2012-11-30

Iron is a limiting nutrient in many parts of the oceans, including the unproductive regions of the Southern Ocean. Although the dominant fraction of the marine iron pool occurs in the form of solid-phase particles, its chemical speciation and mineralogy are challenging to characterize on a regional scale. We describe a diverse array of iron particles, ranging from 20 to 700 nanometers in diameter, in the waters of the Southern Ocean euphotic zone. Distinct variations in the oxidation state and composition of these iron particles exist between the coasts of South Africa and Antarctica, with different iron pools occurring in different frontal zones. These speciation variations can result in solubility differences that may affect the production of bioavailable dissolved iron.

AS SPECIATION AND EFFECTS OF PH AND PHOSPHATE ON THE MOBILIZATION OF AS IN SOILS FROM A LEAD SMELTING SITE. PUBLISHED IN ADVANCED PHOTON SOURCE ACTIVITY REPORT 2003.

EPA Science Inventory

Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and mineralogy were analyzed as a function of depth and surface distribution using bulk and microprobe XAS. These results were c...

Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies.

PubMed

Chen, Chunmei; Kukkadapu, Ravi K; Lazareva, Olesya; Sparks, Donald L

2017-07-18

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57 Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

Reassessing the ratio of glyoxal to formaldehyde as an indicator of hydrocarbon precursor speciation

NASA Astrophysics Data System (ADS)

Kaiser, J.; Wolfe, G. M.; Min, K. E.; Brown, S. S.; Miller, C. C.; Jacob, D. J.; deGouw, J. A.; Graus, M.; Hanisco, T. F.; Holloway, J.; Peischl, J.; Pollack, I. B.; Ryerson, T. B.; Warneke, C.; Washenfelder, R. A.; Keutsch, F. N.

2015-07-01

The yield of formaldehyde (HCHO) and glyoxal (CHOCHO) from oxidation of volatile organic compounds (VOCs) depends on precursor VOC structure and the concentration of NOx (NOx = NO + NO2). Previous work has proposed that the ratio of CHOCHO to HCHO (RGF) can be used as an indicator of precursor VOC speciation, and absolute concentrations of the CHOCHO and HCHO as indicators of NOx. Because this metric is measurable by satellite, it is potentially useful on a global scale; however, absolute values and trends in RGF have differed between satellite and ground-based observations. To investigate potential causes of previous discrepancies and the usefulness of this ratio, we present measurements of CHOCHO and HCHO over the southeastern United States (SE US) from the 2013 SENEX (Southeast Nexus) flight campaign, and compare these measurements with OMI (Ozone Monitoring Instrument) satellite retrievals. High time-resolution flight measurements show that high RGF is associated with monoterpene emissions, low RGF is associated with isoprene oxidation, and emissions associated with oil and gas production can lead to small-scale variation in regional RGF. During the summertime in the SE US, RGF is not a reliable diagnostic of anthropogenic VOC emissions, as HCHO and CHOCHO production are dominated by isoprene oxidation. Our results show that the new CHOCHO retrieval algorithm reduces the previous disagreement between satellite and in situ RGF observations. As the absolute values and trends in RGF observed during SENEX are largely reproduced by OMI observations, we conclude that satellite-based observations of RGF can be used alongside knowledge of land use as a global diagnostic of dominant hydrocarbon speciation.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE PAGES

Bone, Sharon E.; Dynes, James J.; Cliff, John; ...

2017-01-09

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Speciation of Reactive Sulfur Species and their Reactions with Alkylating Agents: Do we have any clue about what is present inside the cell?

PubMed

Bogdándi, Virág; Ida, Tomoaki; Sutton, Thomas R; Bianco, Christopher; Ditrói, Tamás; Koster, Grielof; Henthorn, Hillary A; Minnion, Magda; Toscano, John P; van der Vliet, Albert; Pluth, Michael D; Feelisch, Martin; Fukuto, Jon M; Akaike, Takaaki; Nagy, Péter

2018-06-17

Posttranslational modifications of cysteine (Cys) residues represent a major aspect of redox biology, and their reliable detection is key in providing mechanistic insights. The metastable character of these modifications and cell lysis-induced artifactual oxidation render current state-of-the-art protocols to rely on alkylation-based stabilization of labile Cys derivatives before cell/tissue rupture. An untested assumption in these procedures is that for all Cys derivatives alkylation rates are faster than their dynamic interchange. However, when the interconversion of Cys derivatives is not rate-limiting, then electrophilic labeling is under Curtin-Hammett control and hence the final alkylated mixture may not represent the speciation that prevailed before alkylation. We here present evidence that in the majority of cases, the speciation of alkylated polysulfide/thiol derivatives indeed depends on the experimental conditions. Our results reveal that alkylation perturbs sulfur speciation in both a concentration- and time-dependent manner, and that strong alkylating agents can cleave polysulfur chains. Moreover, we show that labeling of sulfenic acids with dimedone also affects Cys speciation, suggesting that part of the endogenous pool of products previously believed to represent sulfenic acid species may in fact represent polysulfides. These observations were obtained using buffered aqueous solutions of inorganic-, organic-, cysteine-, glutathione- and GAPDH-polysulfide species. Additional experiments in human plasma and serum revealed that monobromobimane can extract sulfide from the endogenous sulfur pool by shifting speciation equilibria, suggesting caution should be exercised when interpreting experimental results using this tool. We highlight methodological caveats potentially arising from these pitfalls and conclude that current derivatization strategies often fail to adequately capture physiologic speciation of sulfur species. This article is protected by copyright. All rights reserved.

MONITORING THE SPECIATION OF AQUEOUS FREE CHLORINE FROM PH 1-12 WITH RAMAN SPECTROSCOPY TO DETERMINE THE IDENTITY OF THE POTENT LOW-PH OXIDANT

EPA Science Inventory

The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl (equilibrium) OCl- + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2 (aq), a...

The analytical biochemistry of chromium.

PubMed Central

Katz, S A

1991-01-01

The essentiality and carcinogenicity of chromium depend on its chemical form. Oxidation state and solubility are particularly important in determining the biological effects of chromium compounds. For this reason, total chromium measurements are of little value in assessing its nutritional benefits or its toxicological hazards. Aqueous sodium carbonate-sodium hydroxide solutions have been successfully used for extracting hexavalent chromium from a variety of environmental and biological matrices while preserving its oxidation state. Typical recoveries are 90 to 105% in samples spiked with both trivalent and hexavalent chromium. Determination of hexavalent chromium after extraction with sodium carbonate-sodium hydroxide solution, coupled with the determination of total chromium after nitric acid-hydrogen peroxide digestion, has been applied to the evaluation of chromium speciation in airborne particulates, sludges, and biological tissues. PMID:1935842

Solid-Phase Speciation of Arsenic As the Primary Control on Dissolved As Concentrations in a Glacial Aquifer System: Quantifying Speciation of Arsenic in Glacial Aquifer Solids with μXAS Mapping.

NASA Astrophysics Data System (ADS)

Nicholas, S. L.; Gowan, A. S.; Knaeble, A. R.; Erickson, M. L.; Woodruff, L. G.; Marcus, M.; Toner, B. M.

2014-12-01

Western Minnesota, USA, is a regional locus of drinking-water wells with high arsenic (As) (As>10µgL-1). Arsenic concentrations vary widely among neighboring wells with otherwise similar water chemistry [1,2]. As(III) should be the most mobile As species in Minnesota well waters (median Eh in As affected wells is -50mV). This As is geogenic, sourced from glacial deposits derived from Cretaceous sedimentary bedrock (dolostone, limestone, shale). Our hypothesis is that As speciation in the solid phase is the important factor controlling the introduction of As to groundwater—more significant in this region than absolute As concentrations or landscape variability. Our previous research used micro-X-ray absorption spectroscopy (µXAS) speciation mapping [3] on archived glacial tills (stored dry at room temperature in air). µXAS results from this material showed that As in a reduced chemical state within the till aquitard is spatially correlated with iron sulfide at the micron scale. Conversley, As in aquifer sediments was mainly oxidized As(V). At the aquifer-aquitard contact As was observed as a mixture of both reduced and oxidized forms. This suggests that the aquifer-aquitard contact is a geochemically active zone in which reduced As species present within glacial till are converted to As(V) through complex redox processes, and subsequently release into aquifer sediments. Our current research applies the same methods to describe As speciation in samples collected from fresh cores of glacial sediment and frozen under argon in the field. Preliminary results are similar to our previous work in that As is, in general, more reduced in aquitard sediments, and more oxidized at the contact and in aquifer sediments. Arsenic(III) was preserved as a minor consitutent in ambient archived cores but is a more significant constituent in fresh, anaerobically preserved cores. Results will be presented comparing anaerobic samples with ambient-air aliquots of the same sample to document changes in the relative abundance of As species depending on sample preservation. This work was supported by LBNL-ALS, ANL-APS, USGS-MNWSC, MGS, and CURA. [1]Berndt & Soule (1999) Minnesota Arsenic Research Study: Report on Geochemistry. [2] Erickson & Barnes (2005) Water Research 39 4029-4039. [3] Toner et al. (2014) Env. Chem. 11 4-9.

Layer speciation and electronic structure investigation of freestanding hexagonal boron nitride nanosheets

NASA Astrophysics Data System (ADS)

WangEqual Contribution To This Work., Jian; Wang, Zhiqiang; Cho, Hyunjin; Kim, Myung Jong; Sham, T. K.; Sun, Xuhui

2015-01-01

Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared.Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04445b

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

PubMed

Li, Dien; Seaman, John C; Chang, Hyun-Shik; Jaffe, Peter R; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I

2014-05-01

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

Selenium speciation in phosphate mine soils and evaluation of a sequential extraction procedure using XAFS.

PubMed

Favorito, Jessica E; Luxton, Todd P; Eick, Matthew J; Grossl, Paul R

2017-10-01

Selenium is a trace element found in western US soils, where ingestion of Se-accumulating plants has resulted in livestock fatalities. Therefore, a reliable understanding of Se speciation and bioavailability is critical for effective mitigation. Sequential extraction procedures (SEP) are often employed to examine Se phases and speciation in contaminated soils but may be limited by experimental conditions. We examined the validity of a SEP using X-ray absorption spectroscopy (XAS) for both whole and a sequence of extracted soils. The sequence included removal of soluble, PO 4 -extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analyses indicated Se(0) and Se(-II) predominated, with lower amounts of Se(IV) present, related to carbonates and Fe-oxides. Oxidized Se species were more elevated and residual/elemental Se was lower than previous SEP results from ICP-AES suggested. For soils from the SEP sequence, XANES results indicated only partial recovery of carbonate, Fe-oxide and organic Se. This suggests Se was incompletely removed during designated extractions, possibly due to lack of mineral solubilization or reagent specificity. Selenium fractions associated with Fe-oxides were reduced in amount or removed after using hydroxylamine HCl for most soils examined. XANES results indicate partial dissolution of solid-phases may occur during extraction processes. This study demonstrates why precautions should be taken to improve the validity of SEPs. Mineralogical and chemical characterizations should be completed prior to SEP implementation to identify extractable phases or mineral components that may influence extraction effectiveness. Sequential extraction procedures can be appropriately tailored for reliable quantification of speciation in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

PubMed

Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne

2015-09-01

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Chunmei; Kukkadapu, Ravi K.; Lazareva, Olesya

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased themore » crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.« less

Synchrotron Speciation Of Silver And Zinc Oxide Nanoparticles Aged In A Kaolin Suspension

EPA Science Inventory

Assessments of the environmental fate and mobility of nanoparticles must consider the behavior of nanoparticles in relevant environmental systems that may result in speciation changes over time. Environmental conditions may act on nanoparticles to change their size, shape, and s...

Speciated Elemental and Isotopic Characterization of Atmospheric Aerosols - Recent Advances

NASA Astrophysics Data System (ADS)

Shafer, M.; Majestic, B.; Schauer, J.

2007-12-01

Detailed elemental, isotopic, and chemical speciation analysis of aerosol particulate matter (PM) can provide valuable information on PM sources, atmospheric processing, and climate forcing. Certain PM sources may best be resolved using trace metal signatures, and elemental and isotopic fingerprints can supplement and enhance molecular maker analysis of PM for source apportionment modeling. In the search for toxicologically relevant components of PM, health studies are increasingly demanding more comprehensive characterization schemes. It is also clear that total metal analysis is at best a poor surrogate for the bioavailable component, and analytical techniques that address the labile component or specific chemical species are needed. Recent sampling and analytical developments advanced by the project team have facilitated comprehensive characterization of even very small masses of atmospheric PM. Historically; this level of detail was rarely achieved due to limitations in analytical sensitivity and a lack of awareness concerning the potential for contamination. These advances have enabled the coupling of advanced chemical characterization to vital field sampling approaches that typically supply only very limited PM mass; e.g. (1) particle size-resolved sampling; (2) personal sampler collections; and (3) fine temporal scale sampling. The analytical tools that our research group is applying include: (1) sector field (high-resolution-HR) ICP-MS, (2) liquid waveguide long-path spectrophotometry (LWG-LPS), and (3) synchrotron x-ray absorption spectroscopy (sXAS). When coupled with an efficient and validated solubilization method, the HR-ICP-MS can provide quantitative elemental information on over 50 elements in microgram quantities of PM. The high mass resolution and enhanced signal-to-noise of HR-ICP-MS significantly advance data quality and quantity over that possible with traditional quadrupole ICP-MS. The LWG-LPS system enables an assessment of the soluble/labile components of PM, while simultaneously providing critical oxidation state speciation data. Importantly, the LWG- LPS can be deployed in a semi-real-time configuration to probe fine temporal scale variations in atmospheric processing or sources of PM. The sXAS is providing complementary oxidation state speciation of bulk PM. Using examples from our research; we will illustrate the capabilities and applications of these new methods.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Kukkadapu, Ravi K.; Livi, Kenneth J. T.

The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption nearmore » edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the formation of Fe(III)-(hydr)oxides plays a very important role in reducing As mobility.« less

FUNDAMENTALS OF MERCURY SPECIATION AND CONTROL IN COAL-FIRED BOILERS

EPA Science Inventory

The report describes the progress of an experimental investigation of the speciation of mercury in simulated coal combustion flue gasses. The effects of flue gas parameters and coal fly ash on the oxidation of elemental mercury (Hgo) in the presence of hydrogen chloride (HCl) in ...

Influence of a soil enzyme on iron-cyanide complex speciation and mineral adsorption.

PubMed

Zimmerman, Andrew R; Kang, Dong-Hee; Ahn, Mi-Youn; Hyun, Seunghun; Banks, M Katherine

2008-01-01

Cyanide is commonly found as ferrocyanide [Fe(II)(CN)(6)](-4) and in the more mobile form, ferricyanide [Fe(III)(CN)(6)](-3) in contaminated soils and sediments. Although soil minerals may influence ferrocyanide speciation, and thus mobility, the possible influence of soil enzymes has not been examined. In a series of experiments conducted under a range of soil-like conditions, laccase, a phenoloxidase enzyme derived from the fungi Trametes versicolor, was found to exert a large influence on iron-cyanide speciation and mobility. In the presence of laccase, up to 93% of ferrocyanide (36-362ppm) was oxidized to ferricyanide within 4h. No significant effect of pH (3.6 and 6.2) or initial ferrocyanide concentration on the extent or rate of oxidation was found and ferrocyanide oxidation did not occur in the absence of laccase. Relative to iron-cyanide-mineral systems without laccase, ferrocyanide adsorption to aluminum hydroxide and montmorillonite decreased in the presence of laccase and was similar to or somewhat greater than that of ferricyanide without laccase. Laccase-catalyzed conversion of ferrocyanide to ferricyanide was extensive though up to 33% of the enzyme was mineral-bound. These results demonstrate that soil enzymes can play a major role in ferrocyanide speciation and mobility. Biotic soil components must be considered as highly effective oxidation catalysts that may alter the mobility of metals and metal complexes in soil. Immobilized enzymes should also be considered for use in soil metal remediation efforts.

Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report, July-September 1984

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jordan, J.; Talbott, J.

1984-01-01

Task 1. Methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2. Methods development for the speciation of dithionite and polythionates. Work on Task 2 has been completed in June 1984 and has been reported accordingly in DOE/PC/40783-T15. Task 3. Total accounting of the sulfur balance in representative samples of synfuel process streams. A systematic and critical comparison of results, obtained in the analysis of sulfur moieties in representative samples of coal conversion process streams, revealed the following general trends. (a) In specimens of highmore » pH (9-10) and low redox potential (-0.3 to -0.4 volt versus NHE) sulfidic and polysulfidic sulfur moieties predominate. (b) In process streams of lower pH and more positive redox potential, higher oxidation states of sulfur (notably sulfate) account for most of the total sulfur present. (c) Oxidative wastewater treatment procedures by the PETC stripping process convert lower oxidation states of sulfur into thiosulfate and sulfate. In this context, remarkable similarities were observed between liquefaction and gasification process streams. However, the thiocyanate present in samples from the Grand Forks gasifier were impervious to the PETC stripping process. (d) Total sulfur contaminant levels in coal conversion process stream wastewater samples are primarily determined by the abundance of sulfur in the coal used as starting material than by the nature of the conversion process (liquefaction or gasification). 13 references.« less

A COMPUTATIONAL AND EXPERIMENTAL STUDY OF MERCURY SPECIATION AS FACILITATED BY THE DEACON PROCESS

EPA Science Inventory

The paper gives results of a computational and experimental study of mercury (Hg) speciation as facilitated by the Deacon process. Fly ashes that contain trace cupric or ferric oxide are effective catalysts for elemental mercury (Hg) conversion to mercuric chloride in the presenc...

Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy.

PubMed

Holden, William M; Seidler, Gerald T; Cheah, Singfoong

2018-05-30

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33 S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Kα XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.

Sulfur Speciation in Biochars by Very High Resolution Benchtop Ka X-Ray Emission Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheah, Singfoong; Holden, William M.; Seidler, Gerald T.

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given bymore » benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.« less

New Technique for Speciation of Uranium in Sediments Following Acetate-Stimulated Bioremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

2011-06-22

Acetate-stimulated bioremediation is a promising new technique for sequestering toxic uranium contamination from groundwater. The speciation of uranium in sediments after such bioremediation attempts remains unknown as a result of low uranium concentration, and is important to analyzing the stability of sequestered uranium. A new technique was developed for investigating the oxidation state and local molecular structure of uranium from field site sediments using X-Ray Absorption Spectroscopy (XAS), and was implemented at the site of a former uranium mill in Rifle, CO. Glass columns filled with bioactive Rifle sediments were deployed in wells in the contaminated Rifle aquifer and amendedmore » with a hexavalent uranium (U(VI)) stock solution to increase uranium concentration while maintaining field conditions. This sediment was harvested and XAS was utilized to analyze the oxidation state and local molecular structure of the uranium in sediment samples. Extended X-Ray Absorption Fine Structure (EXAFS) data was collected and compared to known uranium spectra to determine the local molecular structure of the uranium in the sediment. Fitting was used to determine that the field site sediments did not contain uraninite (UO{sub 2}), indicating that models based on bioreduction using pure bacterial cultures are not accurate for bioremediation in the field. Stability tests on the monomeric tetravalent uranium (U(IV)) produced by bioremediation are needed in order to assess the efficacy of acetate-stimulation bioremediation.« less

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

DOE PAGES

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; ...

2017-07-21

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; Noël, Vincent; Fritsch, Emmanuel; Proux, Olivier; Olivi, Luca; Ploquin, Florian; Morin, Guillaume

2017-11-01

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopy at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. This latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions.

PubMed

Lee, Chun W; Serre, Shannon D; Zhao, Yongxin; Lee, Sung Jun; Hastings, Thomas W

2008-04-01

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.

Selenium Speciation and Management in Wet FGD Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Searcy, K; Richardson, M; Blythe, G

2012-02-29

This report discusses results from bench- and pilot-scale simulation tests conducted to determine the factors that impact selenium speciation and phase partitioning in wet FGD systems. The selenium chemistry in wet FGD systems is highly complex and not completely understood, thus extrapolation and scale-up of these results may be uncertain. Control of operating parameters and application of scrubber additives have successfully demonstrated the avoidance or decrease of selenite oxidation at the bench and pilot scale. Ongoing efforts to improve sample handling methods for selenium speciation measurements are also discussed. Bench-scale scrubber tests explored the impacts of oxidation air rate, tracemore » metals, scrubber additives, and natural limestone on selenium speciation in synthetic and field-generated full-scale FGD liquors. The presence and concentration of redox-active chemical species as well as the oxidation air rate contribute to the oxidation-reduction potential (ORP) conditions in FGD scrubbers. Selenite oxidation to the undesirable selenate form increases with increasing ORP conditions, and decreases with decreasing ORP conditions. Solid-phase manganese [Mn(IV)] appeared to be the significant metal impacting the oxidation of selenite to selenate. Scrubber additives were tested for their ability to inhibit selenite oxidation. Although dibasic acid and other scrubber additives showed promise in early clear liquor (sodium based and without calcium solids) bench-scale tests, these additives did not show strong inhibition of selenite oxidation in tests with higher manganese concentrations and with slurries from full-scale wet FGD systems. In bench-tests with field liquors, addition of ferric chloride at a 250:1 iron-to-selenium mass ratio sorbed all incoming selenite to the solid phase, although addition of ferric salts had no impact on native selenate that already existed in the field slurry liquor sample. As ORP increases, selenite may oxidize to selenate more rapidly than it sorbs to ferric solids. Though it was not possible to demonstrate a decrease in selenium concentrations to levels below the project'ale testing were evident at the pilot scale. Specifically, reducing oxidation air rate and ORP tends to either retain selenium as selenite in the liquor or shift selenium phase partitioning to the solid phase. Oxidation air flow rate control may be one option for managing selenium behavior in FGD scrubbers. Units that cycle load widely may find it more difficult to impact ORP conditions with oxidation air flow rate control alone. Because decreasing oxidation air rates to the reaction tank showed that all new selenium reported to the solids, the addition of ferric chloride to the pilot scrubber could not show further improvements in selenium behavior. Ferric chloride addition did shift mercury to the slurry solids, specifically to the fine particles. Several competing pathways may govern the reporting of selenium to the slurry solids: co-precipitation with gypsum into the bulk solids and sorption or co-precipitation with iron into the fine particles. Simultaneous measurement of selenium and mercury behavior suggests a holistic management strategy is best to optimize the fate of both of these elements in FGD waters. Work conducted under this project evaluated sample handling and analytical methods for selenium speciation in FGD waters. Three analytical techniques and several preservation methods were employed. Measurements of selenium speciation over time indicated that for accurate selenium speciation, it is best to conduct measurements on unpreserved, filtered samples as soon after sampling as possible. The capital and operating costs for two selenium management strategies were considered: ferric chloride addition and oxidation air flow rate control. For ferric chloride addition, as might be expected the reagent makeup costs dominate the overall costs, and range from 0.22 to 0.29 mills/kWh. For oxidation air flow rate control, a cursory comparison of capital costs and turndown capabilities for multi-stage and single-stage centrifugal blowers and several flow control methods was completed. For greenfield systems, changing the selection of blower type and flow control method may have payback periods of 4 to 5 years or more if based on energy savings alone. However, the benefits to managing redox chemistry in the scrubber could far outweigh the savings in electricity costs under some circumstances.« less

Further refinement of 17O TRAPDOR NMR methods for determining oxygen speciation in multi-component oxide glasses

NASA Astrophysics Data System (ADS)

LaComb, M.; Stebbins, J. F.

2017-12-01

Solid state nuclear magnetic resonance (NMR) spectroscopy has often been utilized to determine network speciation in oxide glasses, typically using NMR-active nuclides such as 11B, 27Al and 17O. High field strength magnets allow for visible separation between bridging (BO) and non-bridging oxygens (NBO) in 17O magic-angle spinning (MAS) NMR spectra, but many questions remain due to limited ability to directly observe NBO associated with silicon, boron or aluminum in ternary glass systems with MAS NMR techniques. Recent studies have utilized the combination of 17O{27Al} and 17O{11B} TRAnsfer of Population in DOuble-Resonance (TRAPDOR) NMR to attempt to separate out resonances for these different bridging and non-bridging oxygen species in multicomponent calcium aluminosilicate and aluminoborosilicate glasses and rare-earth aluminoborosilicates. With improved technology and better resolution of spectral components we were able to expand this study to a wider range of calcium aluminosilicate, aluminoborate and aluminoborosilicate glasses and further separate out resonances for both bridging and non-bridging oxygens coordinated with aluminum, boron and/or silicon cations in these glasses.

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Quantification of trace elements and speciation of iron in atmospheric particulate matter

NASA Astrophysics Data System (ADS)

Upadhyay, Nabin

Trace metal species play important roles in atmospheric redox processes and in the generation of oxidants in cloud systems. The chemical impact of these elements on atmospheric and cloud chemistry is dependent on their occurrence, solubility and speciation. First, analytical protocols have been developed to determine trace elements in particulate matter samples collected for carbonaceous analysis. The validated novel protocols were applied to the determination of trace elements in particulate samples collected in the remote marine atmosphere and urban areas in Arizona to study air pollution issues. The second part of this work investigates on solubility and speciation in environmental samples. A detailed study on the impact of the nature and strength of buffer solutions on solubility and speciation of iron lead to a robust protocol, allowing for comparative measurements in matrices representative of cloud water conditions. Application of this protocol to samples from different environments showed low iron solubility (less than 1%) in dust-impacted events and higher solubility (5%) in anthropogenically impacted urban samples. In most cases, Fe(II) was the dominant oxidation state in the soluble fraction of iron. The analytical protocol was then applied to investigate iron processing by fogs. Field observations showed that only a small fraction (1%) of iron was scavenged by fog droplets for which each of the soluble and insoluble fraction were similar. A coarse time resolution limited detailed insights into redox cycling within fog system. Overall results suggested that the major iron species in the droplets was Fe(1I) (80% of soluble iron). Finally, the occurrence and sources of emerging organic pollutants in the urban atmosphere were investigated. Synthetic musk species are ubiquitous in the urban environment (less than 5 ng m-3) and investigations at wastewater treatment plants showed that wastewater aeration basins emit a substantial amount of these species to the atmosphere.

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, Lei; Wang, Shuxiao; Wu, Qingru; Wang, Fengyang; Lin, Che-Jen; Zhang, Leiming; Hui, Mulin; Yang, Mei; Su, Haitao; Hao, Jiming

2016-02-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, waste incinerators, biomass burning and so on. Mercury in coal, ores, and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of Hg0 to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g., TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher Hg0 fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron and/or steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, L.; Wang, S. X.; Wu, Q. R.; Wang, F. Y.; Lin, C.-J.; Zhang, L. M.; Hui, M. L.; Hao, J. M.

2015-11-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, municipal solid waste incinerators, and biomass burning. Mercury in coal, ores and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of gaseous elemental mercury (Hg0) to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g.,TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron/steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films.

PubMed

Cusnir, Ruslan; Steinmann, Philipp; Christl, Marcus; Bochud, François; Froidevaux, Pascal

2015-11-09

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can potentially contribute to the exposure of biota and humans. The diffusive gradients in thin films technique is introduced here for in-situ measurements of Pu bioavailability and speciation. A diffusion cell constructed for laboratory experiments with Pu and the newly developed protocol make it possible to simulate the environmental behavior of Pu in model solutions of various chemical compositions. Adjustment of the oxidation states to Pu(IV) and Pu(V) described in this protocol is essential in order to investigate the complex redox chemistry of plutonium in the environment. The calibration of this technique and the results obtained in the laboratory experiments enable to develop a specific DGT device for in-situ Pu measurements in freshwaters. Accelerator-based mass-spectrometry measurements of Pu accumulated by DGTs in a karst spring allowed determining the bioavailability of Pu in a mineral freshwater environment. Application of this protocol for Pu measurements using DGT devices has a large potential to improve our understanding of the speciation and the biological transfer of Pu in aquatic ecosystems.

Degassing of reduced carbon from planetary basalts.

PubMed

Wetzel, Diane T; Rutherford, Malcolm J; Jacobsen, Steven D; Hauri, Erik H; Saal, Alberto E

2013-05-14

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential.

Chemical transformations during aging of zerovalent iron nanoparticles in the presence of common groundwater dissolved constituents.

PubMed

Reinsch, Brian C; Forsberg, Brady; Penn, R Lee; Kim, Christopher S; Lowry, Gregory V

2010-05-01

Nanoscale zerovalent iron (NZVI) that was aged in simulated groundwater was evaluated for alterations in composition and speciation over 6 months to understand the possible transformations NZVI could undergo in natural waters. NZVI was exposed to 10 mN of various common groundwater anions (Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), and HCO(3)(-)) or to dissolved oxygen (saturated, approximately 9 mg/L). Fresh and exposed NZVI samples, along with Fe-oxide model compounds, were then analyzed using synchrotron radiation X-ray absorption spectroscopy (XAS) to yield both relative oxidation state, using the X-ray absorption near edge structure (XANES), and quantitative speciation information regarding the types and proportions of mineral species present, from analysis of the extended X-ray absorption fine structure (EXAFS). Over 1 month of aging the dissolved anions inhibited the oxidation of the NZVI to varying degrees. Aging for 6 months, however, resulted in average oxidation states that were similar to each other regardless of the anion used, except for nitrate. Nitrate passivated the NZVI surface such that even after 6 months of aging the particles retained nearly the same mineral and Fe(0) content as fresh NZVI. Linear least-squares combination fitting (LCF) of the EXAFS spectra for 1 month-aged samples indicated that the oxidized particles remain predominantly a binary phase system containing Fe(0) and Fe(3)O(4), while the 6 month aged samples contained additional mineral phases such as vivianite (Fe(3)(PO(4))(2).8H(2)O) and iron sulfate species, possibly schwertmannite (Fe(3+)(16)O(16)(OH,SO(4))(12-13).10-12H(2)O). The presence of these additional mineral species was confirmed using synchrotron-based X-ray diffraction (XRD). NZVI exposed to water saturated with dissolved oxygen showed a rapid (<24 h) loss of Fe(0) and evolved both magnetite and maghemite (gamma-Fe(2)O(3)) within the oxide layer. These findings have implications toward the eventual fate, transport, and toxicity of NZVI used for groundwater remediation.

Cerium anomaly at microscale in fossils.

PubMed

Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

2015-09-01

Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies.

Detecting Hidden Diversification Shifts in Models of Trait-Dependent Speciation and Extinction.

PubMed

Beaulieu, Jeremy M; O'Meara, Brian C

2016-07-01

The distribution of diversity can vary considerably from clade to clade. Attempts to understand these patterns often employ state-dependent speciation and extinction models to determine whether the evolution of a particular novel trait has increased speciation rates and/or decreased extinction rates. It is still unclear, however, whether these models are uncovering important drivers of diversification, or whether they are simply pointing to more complex patterns involving many unmeasured and co-distributed factors. Here we describe an extension to the popular state-dependent speciation and extinction models that specifically accounts for the presence of unmeasured factors that could impact diversification rates estimated for the states of any observed trait, addressing at least one major criticism of BiSSE (Binary State Speciation and Extinction) methods. Specifically, our model, which we refer to as HiSSE (Hidden State Speciation and Extinction), assumes that related to each observed state in the model are "hidden" states that exhibit potentially distinct diversification dynamics and transition rates than the observed states in isolation. We also demonstrate how our model can be used as character-independent diversification models that allow for a complex diversification process that is independent of the evolution of a character. Under rigorous simulation tests and when applied to empirical data, we find that HiSSE performs reasonably well, and can at least detect net diversification rate differences between observed and hidden states and detect when diversification rate differences do not correlate with the observed states. We discuss the remaining issues with state-dependent speciation and extinction models in general, and the important ways in which HiSSE provides a more nuanced understanding of trait-dependent diversification. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Spatio-temporal Distribution and Chemical Speciation of Iron and Manganese in Sediments from Lake Aha, China

NASA Astrophysics Data System (ADS)

Liu, Feng; Hu, Jiwei; Qin, Fanxin; Jiang, Cuihong; Huang, Xianfei; Deng, Jiajun; Li, Cunxiong

2010-11-01

This paper reports an investigation on pollution and potential risk on elements of iron (Fe) and manganese (Mn) in sediments from Lake Aha, which is a drinking-water source for Guiyang City, the capital of Guizhou Province in southwestern China. In the present research, chemical speciation of Fe and Mn in sediments from the lake was studied based on the sequential extraction procedure developed by Tessier et al.. The results obtained from the study are as follows. The average values of total Fe were 47617 mg/kg and 70325 mg/kg in sediments from the lake in summer and winter respectively, and its speciation consisted mainly of residual and Fe-Mn oxides fractions. The amounts of total Fe and the distribution of its speciation in the sediments should be affected by effluents from a large quantity of deserted coal mines in the lake basin in summer and winter. The average values of total Mn were 7996 mg/kg and 1753 mg/kg in summer and winter respectively, and its speciation is primarily comprised of carbonate and Fe-Mn oxides fractions. The amounts of total Mn and its distribution in different fractions in the sediments were believed to be primarily influenced by effluents from those deserted coal mines in summer and by the condition of redox interface in winter.

APPLICATION OF SAMPLE PRE-OXIDATION OF ARSENITE IN HUMAN URINE PRIOR TO SPECIATON VIA ON-LINE PHOTO-OXIDATION WITH MEMBRANE HYDRIDE GENRATION AND ICP-MS DETECTION

EPA Science Inventory

A pre-oxidation procedure which converts arsenite (AS(III)) to arsenate (As(VVV)) was investigated in urinary arsenic speciation prior to on-line photo-oxidation hydride-generation with ICP-MS detection. This sample pre-oxidation method eliminates As(III) and As(V) preservation c...

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Adeline R.; Silva, Silmara Costa; Webb, Samuel M.

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms weremore » fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.« less

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

DOE PAGES

Lopez, Adeline R.; Silva, Silmara Costa; Webb, Samuel M.; ...

2017-11-02

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms weremore » fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.« less

Volcanic gas composition, metal dispersion and deposition during explosive volcanic eruptions on the Moon

NASA Astrophysics Data System (ADS)

Renggli, C. J.; King, P. L.; Henley, R. W.; Norman, M. D.

2017-06-01

The transport of metals in volcanic gases on the Moon differs greatly from their transport on the Earth because metal speciation depends largely on gas composition, temperature, pressure and oxidation state. We present a new thermochemical model for the major and trace element composition of lunar volcanic gas during pyroclastic eruptions of picritic magmas calculated at 200-1500 °C and over 10-9-103 bar. Using published volatile component concentrations in picritic lunar glasses, we have calculated the speciation of major elements (H, O, C, Cl, S and F) in the coexisting volcanic gas as the eruption proceeds. The most abundant gases are CO, H2, H2S, COS and S2, with a transition from predominantly triatomic gases to diatomic gases with increasing temperatures and decreasing pressures. Hydrogen occurs as H2, H2S, H2S2, HCl, and HF, with H2 making up 0.5-0.8 mol fractions of the total H. Water (H2O) concentrations are at trace levels, which implies that H-species other than H2O need to be considered in lunar melts and estimates of the bulk lunar composition. The Cl and S contents of the gas control metal chloride gas species, and sulfide gas and precipitated solid species. We calculate the speciation of trace metals (Zn, Ga, Cu, Pb, Ni, Fe) in the gas phase, and also the pressure and temperature conditions at which solids form from the gas. During initial stages of the eruption, elemental gases are the dominant metal species. As the gas loses heat, chloride and sulfide species become more abundant. Our chemical speciation model is applied to a lunar pyroclastic eruption model with isentropic gas decompression. The relative abundances of the deposited metal-bearing solids with distance from the vent are predicted for slow cooling rates (<5 °C/s). Close to a volcanic vent we predict native metals are deposited, whereas metal sulfides dominate with increasing distance from the vent. Finally, the lunar gas speciation model is compared with the speciation of a H2O-, CO2- and Cl-rich volcanic gas from Erta Ale volcano (Ethiopia) as an analogy for more oxidized planetary eruptions. In the terrestrial Cl-rich gas the metals are predominantly transported as chlorides, as opposed to metallic vapors and sulfides in the lunar gas. Due to the presence of Cl-species, metal transport is more efficient in the volcanic gas from Erta Ale compared to the Moon.

Acid Sulfate Alteration in Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Ming, D. W.; Catalano, J. G.

2016-01-01

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

PubMed

Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

2017-02-08

We demonstrate herein that Mn 3+ and not Mn 2+ , as commonly accepted, is the dominant dissolved manganese cation in LiPF 6 -based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn 3+ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn 3+ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn 3+ occurs at a very slow rate.

Sensitivity model study of regional mercury dispersion in the atmosphere

NASA Astrophysics Data System (ADS)

Gencarelli, Christian N.; Bieser, Johannes; Carbone, Francesco; De Simone, Francesco; Hedgecock, Ian M.; Matthias, Volker; Travnikov, Oleg; Yang, Xin; Pirrone, Nicola

2017-01-01

Atmospheric deposition is the most important pathway by which Hg reaches marine ecosystems, where it can be methylated and enter the base of food chain. The deposition, transport and chemical interactions of atmospheric Hg have been simulated over Europe for the year 2013 in the framework of the Global Mercury Observation System (GMOS) project, performing 14 different model sensitivity tests using two high-resolution three-dimensional chemical transport models (CTMs), varying the anthropogenic emission datasets, atmospheric Br input fields, Hg oxidation schemes and modelling domain boundary condition input. Sensitivity simulation results were compared with observations from 28 monitoring sites in Europe to assess model performance and particularly to analyse the influence of anthropogenic emission speciation and the Hg0(g) atmospheric oxidation mechanism. The contribution of anthropogenic Hg emissions, their speciation and vertical distribution are crucial to the simulated concentration and deposition fields, as is also the choice of Hg0(g) oxidation pathway. The areas most sensitive to changes in Hg emission speciation and the emission vertical distribution are those near major sources, but also the Aegean and the Black seas, the English Channel, the Skagerrak Strait and the northern German coast. Considerable influence was found also evident over the Mediterranean, the North Sea and Baltic Sea and some influence is seen over continental Europe, while this difference is least over the north-western part of the modelling domain, which includes the Norwegian Sea and Iceland. The Br oxidation pathway produces more HgII(g) in the lower model levels, but overall wet deposition is lower in comparison to the simulations which employ an O3 / OH oxidation mechanism. The necessity to perform continuous measurements of speciated Hg and to investigate the local impacts of Hg emissions and deposition, as well as interactions dependent on land use and vegetation, forests, peat bogs, etc., is highlighted in this study.

XANES Identification of Plutonium Speciation in RFETS Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

LoPresti, V.; Conradson, S.D.; Clark, D.L.

2009-06-03

Using primarily X-ray absorption near edge spectroscopy (XANES) with standards run in tandem with samples, probable plutonium speciation was determined for 13 samples from contaminated soil, acid-splash or fire-deposition building interior surfaces, or asphalt pads from the Rocky Flats Environmental Technology Site (RFETS). Save for extreme oxidizing situations, all other samples were found to be of Pu(IV) speciation, supporting the supposition that such contamination is less likely to show mobility off site. EXAFS analysis conducted on two of the 13 samples supported the validity of the XANES features employed as determinants of the plutonium valence.

Bioconcentration and arsenic speciation analysis in ragworm, Hediste diversicolor (Muller 1776).

PubMed

Gaion, Andrea; Scuderi, Alice; Pellegrini, David; Sartori, Davide

2013-01-01

This study focused on bioconcentrations of arsenic in Hediste diversicolor (Müller 1776) after exposure to three different molecule solutions: arsenate, dimethyl-arsinate and arsenobetaine. Speciation analysis was carried out after exposing the organisms to these solutions in order to investigate their arsenic biotransformation capacity. Arsenic reached to the maximum level in these tissues after 15 days' exposure to a solution of 100 μg L(-1) of arsenobetaine, although a significant increase was obtained in worms exposed to arsenate. Speciation analysis shows that trimethyl-arsine oxide is the slowest detoxification phase recorded in experiment.

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacold, J. I.; Lukens, W. W.; Booth, C. H.

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variationsmore » among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacold, J. I.; Lukens, W. W.; Booth, C. H.

We report that nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. Wemore » find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. Lastly, the resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

DOE PAGES

Pacold, J. I.; Lukens, W. W.; Booth, C. H.; ...

2016-05-18

We report that nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. Wemore » find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. Lastly, the resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

NASA Astrophysics Data System (ADS)

Pacold, J. I.; Lukens, W. W.; Booth, C. H.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

2016-05-01

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

Redox change during magma ascent; Observation from three volcanoes and implication for gas monitoring

NASA Astrophysics Data System (ADS)

Moussallam, Yves; Oppenheimer, Clive; Schipper, Ian C.; Hartley, Magaret; Scaillet, Bruno; Gaillard, Fabrice; Peters, Nial; Kyle, Phil

2015-04-01

The oxidation state of volcanic gases dictates their speciation and hence their reactivity in the atmosphere. It has become increasingly recognized that the oxidation state of a magma can be strongly affected by degassing. The oxidation state of gases will equally be impacted and the composition of gases emitted by volcanoes will therefore be function of the magma degassing history. This presentation will show results from three volcanoes where the oxidation state of the magma has been tracked during degassing. At Erebus and Laki we used Fe X-ray absorption near-edge structure spectroscopy (XANES) on extensive suites of melt inclusions and glasses, while at Surtsey we used S-Kα peak shifts measurements by electron microprobe (EPMA) on melt inclusions, embayment and glasses. At all three locations we found that a strong reduction of both Fe and S is associated with magma ascent. At Erebus this reduction is greatest, corresponding to a fall in magmatic fO2 of more than two log units. We propose that sulfur degassing can explain the observed evolution of the redox state with ascent and show that forward modeling using initial melt composition can successfully predict the composition of the gas phase measured at the surface. We suggest that the redox state of volcanic gases (expressed in term of redox couples: H2O/H2, SO2/H2S and CO2/CO) can be used to monitor the depth of gas-melt segregation at active volcanoes.

Diverse manganese(II)-oxidizing bacteria are prevalent in drinking water systems.

PubMed

Marcus, Daniel N; Pinto, Ameet; Anantharaman, Karthik; Ruberg, Steven A; Kramer, Eva L; Raskin, Lutgarde; Dick, Gregory J

2017-04-01

Manganese (Mn) oxides are highly reactive minerals that influence the speciation, mobility, bioavailability and toxicity of a wide variety of organic and inorganic compounds. Although Mn(II)-oxidizing bacteria are known to catalyze the formation of Mn oxides, little is known about the organisms responsible for Mn oxidation in situ, especially in engineered environments. Mn(II)-oxidizing bacteria are important in drinking water systems, including in biofiltration and water distribution systems. Here, we used cultivation dependent and independent approaches to investigate Mn(II)-oxidizing bacteria in drinking water sources, a treatment plant and associated distribution system. We isolated 29 strains of Mn(II)-oxidizing bacteria and found that highly similar 16S rRNA gene sequences were present in all culture-independent datasets and dominant in the studied drinking water treatment plant. These results highlight a potentially important role for Mn(II)-oxidizing bacteria in drinking water systems, where biogenic Mn oxides may affect water quality in terms of aesthetic appearance, speciation of metals and oxidation of organic and inorganic compounds. Deciphering the ecology of these organisms and the factors that regulate their Mn(II)-oxidizing activity could yield important insights into how microbial communities influence the quality of drinking water. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Favorito, Jessica E.; Luxton, Todd P.; Eick, Matthew J.

Selenium is a trace element found in western US soils, where ingestion of Se-accumulating plants has resulted in livestock fatalities. Therefore, a reliable understanding of Se speciation and bioavailability is critical for effective mitigation. Sequential extraction procedures (SEP) are often employed to examine Se phases and speciation in contaminated soils but may be limited by experimental conditions. We examined the validity of a SEP using X-ray absorption spectroscopy (XAS) for both whole and a sequence of extracted soils. The sequence included removal of soluble, PO4-extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analysesmore » indicated Se(0) and Se(-II) predominated, with lower amounts of Se(IV) present, related to carbonates and Fe-oxides. Oxidized Se species were more elevated and residual/elemental Se was lower than previous SEP results from ICP-AES suggested. For soils from the SEP sequence, XANES results indicated only partial recovery of carbonate, Fe-oxide and organic Se. This suggests Se was incompletely removed during designated extractions, possibly due to lack of mineral solubilization or reagent specificity. Selenium fractions associated with Fe-oxides were reduced in amount or removed after using hydroxylamine HCl for most soils examined. XANES results indicate partial dissolution of solid-phases may occur during extraction processes. This study demonstrates why precautions should be taken to improve the validity of SEPs. Mineralogical and chemical characterizations should be completed prior to SEP implementation to identify extractable phases or mineral components that may influence extraction effectiveness. Sequential extraction procedures can be appropriately tailored for reliable quantification of speciation in contaminated soils.« less

Characterizing Zinc Speciation in Soils from a Smelter-Affected Boreal Forest Ecosystem.

PubMed

Hamilton, Jordan G; Farrell, Richard E; Chen, Ning; Feng, Renfei; Reid, Joel; Peak, Derek

2016-03-01

HudBay Minerals, Inc., has mined and/or processed Zn and Cu ore in Flin Flon, MB, Canada, since the 1930s. The boreal forest ecosystem and soil surrounding these facilities have been severely impacted by mixed metal contamination and HSO deposition. Zinc is one of the most prevalent smelter-derived contaminants and has been identified as a key factor that may be limiting revegetation. Metal toxicity is related to both total concentrations and speciation; therefore, X-ray absorption spectroscopy and X-ray fluorescence mapping were used to characterize Zn speciation in soils throughout the most heavily contaminated areas of the landscape. Zinc speciation was linked to two distinct soil types. Group I soils consist of exposed soils in weathered positions of bedrock outcrops with Zn present primarily as franklinite, a (ZnFeO) spinel mineral. Group II soils are stabilized by an invasive metal-tolerant grass species, with Zn found as a mixture of octahedral (Fe oxides) and tetrahedral Mn oxides) adsorption complexes with a franklinite component. Soil erosion influences Zn speciation through the redistribution of Zn and soil particulates from Group I landscape positions to Group II soils. Despite Group II soils having the highest concentrations of CaCl-extractable Zn, they support metal-tolerant plant growth. The metal-tolerant plants are probably preferentially colonizing these areas due to better soil and nutrient conditions as a result of soil deposition from upslope Group I areas. Zinc concentration and speciation appears to not influence the colonization by metal-tolerant grasses, but the overall soil properties and erosion effects prevent the revegetation by native boreal forest species. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Composition and oxidation state of sulfur in atmospheric particulate matter

NASA Astrophysics Data System (ADS)

Longo, Amelia F.; Vine, David J.; King, Laura E.; Oakes, Michelle; Weber, Rodney J.; Huey, Lewis Gregory; Russell, Armistead G.; Ingall, Ellery D.

2016-10-01

The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS) and X-ray fluorescence (XRF) microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm) analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

A Multi-spectroscopic Investigation of Sulphur Speciation in Silicate Glasses and Slags

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bingham, P.; Connelly, A; Hand, R

2010-01-01

Sulphur K-edge x-ray absorption near-edge structure (XANES), sulphur K{sub {alpha}} and K{sub {beta}} high resolution x-ray emission spectroscopies (XES), electron paramagnetic resonance (EPR) and optical absorption spectroscopies have been used to study the speciation of sulphur in a range of soda-lime-silica glasses and silicate slags. Several inorganic standards with known sulphur oxidation states and structural environments have also been analysed. Results confirm that the average oxidation state of sulphur in glasses decreases, as expected, in the order (colourless>light olive>dark olive>light amber>dark amber). This behaviour is consistent with decreasing S{sup 6+}/{Sigma}S ratio, which has been quantified by linear combination fitting ofmore » XES S K{alpha} spectra, and with analysed sulphur contents which exhibit a characteristic relationship with oxygen partial pressure, pO{sub 2}. A combination of S{sup 6+}, S{sup 5+}, S{sup 4+} and more reduced sulphur species has been detected in olive and amber glasses. The S{sup 4+} and S{sup 5+} species are most evident in olive-coloured glasses produced under moderately reducing conditions that coincide with minimum sulphur solubilities. The reduced form of sulphur, present in all reduced glasses, is interpreted as being present as S{sup 2-} on the basis of XANES, XES, EPR and optical measurements. An alternative interpretation of the data is that there is a continuum of less strongly reduced species, primarily S{sup +} and S{sup 2+}; this interpretation has less merit. In this paper we show that the established relationship that describes sulphur redox only in terms of S{sup 6+} and S{sup 2-}, and which states that only these two species co-exist over a narrow, moderately reducing range of pO{sub 2}, does not fully describe the behaviour of S in the industrial, non-equilibrated glasses studied. Hence this relationship requires slight modification for non-equilibrated systems to explain the existence of intermediate sulphur oxidation states such as S{sup 4+} and S{sup 5+}, particularly within the intermediate pO{sub 2} range that corresponds with sulphur solubility minima.« less

Degassing of reduced carbon from planetary basalts

PubMed Central

Wetzel, Diane T.; Rutherford, Malcolm J.; Jacobsen, Steven D.; Hauri, Erik H.; Saal, Alberto E.

2013-01-01

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential. PMID:23569260

Systematization of the mass spectra for speciation of inorganic salts with static secondary ion mass spectrometry.

PubMed

Van Ham, Rita; Van Vaeck, Luc; Adams, Freddy C; Adriaens, Annemie

2004-05-01

The analytical use of mass spectra from static secondary ion mass spectrometry for the molecular identification of inorganic analytes in real life surface layers and microobjects requires an empirical insight in the signals to be expected from a given compound. A comprehensive database comprising over 50 salts has been assembled to complement prior data on oxides. The present study allows the systematic trends in the relationship between the detected signals and molecular composition of the analyte to be delineated. The mass spectra provide diagnostic information by means of atomic ions, structural fragments, molecular ions, and adduct ions of the analyte neutrals. The prediction of mass spectra from a given analyte must account for the charge state of the ions in the salt, the formation of oxide-type neutrals from oxy salts, and the occurrence of oxidation-reduction processes.

Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

PubMed Central

Jathar, Shantanu H.; Gordon, Timothy D.; Hennigan, Christopher J.; Pye, Havala O. T.; Pouliot, George; Adams, Peter J.; Donahue, Neil M.; Robinson, Allen L.

2014-01-01

Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10–20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y−1 of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

USGS Publications Warehouse

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; Knaeble, Alan R.; Marcus, Matthew A.; Lynch, Joshua K.; Toner, Brandy M.

2017-01-01

e of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (lXAS) approach is developed and applied to rotosonic drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s lXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity observed in the distribution of elevated-As wells.

Elucidating the Chemical Complexity of Organic Aerosol Constituents Measured During the Southeastern Oxidant and Aerosol Study (SOAS)

NASA Astrophysics Data System (ADS)

Yee, L.; Isaacman, G. A.; Spielman, S. R.; Worton, D. R.; Zhang, H.; Kreisberg, N. M.; Wilson, K. R.; Hering, S. V.; Goldstein, A. H.

2013-12-01

Thousands of volatile organic compounds are uniquely created in the atmosphere, many of which undergo chemical transformations that result in more highly-oxidized and often lower vapor pressure species. These species can contribute to secondary organic aerosol, a complex mixture of organic compounds that is still not chemically well-resolved. Organic aerosol collected on filters taken during the Southeastern Oxidant and Aerosol Study (SOAS) constitute hundreds of unique chemical compounds. Some of these include known anthropogenic and biogenic tracers characterized using standardized analytical techniques (e.g. GC-MS, UPLC, LC-MS), but the majority of the chemical diversity has yet to be explored. By employing analytical techniques involving sample derivatization and comprehensive two-dimensional gas chromatography (GC x GC) with high-resolution-time-of-flight mass spectrometry (HR-ToF-MS), we elucidate the chemical complexity of the organic aerosol matrix along the volatility and polarity grids. Further, by utilizing both electron impact (EI) and novel soft vacuum ultraviolet (VUV) ionization mass spectrometry, a greater fraction of the organic mass is fully speciated. The GC x GC-HR-ToF-MS with EI/VUV technique efficiently provides an unprecedented level of speciation for complex ambient samples. We present an extensive chemical characterization and quantification of organic species that goes beyond typical atmospheric tracers in the SOAS samples. We further demonstrate that complex organic mixtures can be chemically deconvoluted by elucidation of chemical formulae, volatility, functionality, and polarity. These parameters provide insight into the sources (anthropogenic vs. biogenic), chemical processes (oxidation pathways), and environmental factors (temperature, humidity), controlling organic aerosol growth in the Southeastern United States.

Chromium in urban sediment particulates: an integrated micro-chemical and XANES study

NASA Astrophysics Data System (ADS)

Taylor, Kevin; Byrne, Patrick; Hudson-Edwards, Karen

2015-04-01

Chromium is generally common within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid phase chemical speciation of Cr in the particles. In this study, we use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK. Cr-bearing grains within RDS are predominantly iron oxide grains, commonly of goethite or haematite mineralogy, but Cr-bearing silicate glass grains are also present. Iron oxide glass grains most likely have sorbed Cr, and derive from the rusting of Cr-steel particles from vehicles. Electron microprobe analysis indicates concentrations of Cr up to 3200 μg/g in these grains, and XANES analysis indicates that Cr(III) is the dominant oxidation state, with some trace amounts of Cr(VI). Cr-bearing grains within aquatic sediments are dominated by alumino-silicate glass grains derived from industrial waste. These grains contain Cr-rich areas with up to 19% Cr2O3 and XANES analysis indicates that Cr is present as Cr(III). The dominance of Cr(III) in these urban particulate grains suggests limited bioavailability or toxicity. However, the presence within two markedly different grain types (iron oxides and silicate glasses) indicates that the long-term geochemical behaviour and environmental risk of RDS and the aquatic sediments studied are likely to be quite different. These findings highlight the importance of understanding sources of metal contaminants in urban environments and the geochemical processes that affect their transfer through the urban sediment cascade and the wider river basin.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

2010-01-01

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Synchrotron speciation of silver and zinc oxide nanoparticles aged in a kaolin suspension.

PubMed

Scheckel, Kirk G; Luxton, Todd P; El Badawy, Amro M; Impellitteri, Christopher A; Tolaymat, Thabet M

2010-02-15

Assessments of the environmental fate and mobility of nanoparticles must consider the behavior of nanoparticles in relevant environmental systems that may result in speciation changes over time. Environmental conditions may act on nanoparticles to change their size, shape, and surface chemistry. Changing these basic characteristics of nanoparticles may result in a final reaction product that is significantly different than the initial nanomaterial. As such, basing long-term risk and toxicity on the initial properties of a nanomaterial may lead to erroneous conclusions if nanoparticles change upon release to the environment. The influence of aging on the speciation and chemical stability of silver and zinc oxide nanoparticles in kaolin suspensions was examined in batch reactors for up to 18 months. Silver nanoparticles remained unchanged in sodium nitrate suspensions; however, silver chloride was identified with the metallic silver nanoparticles in sodium chloride suspensions and may be attributed to an in situ silver chloride surface coating. Zinc oxide nanoparticles were rapidly converted via destabilization/dissolution mechanisms to Zn(2+) inner-sphere sorption complexes within 1 day of reaction and these sorption complexes were maintained through the 12 month aging processes. Chemical and physical alteration of nanomaterials in the environment must be examined to understand fate, mobility, and toxicology.

Defense Coastal/Estuarine Research Program (DCERP) Baseline Monitoring Plan

DTIC Science & Technology

2007-09-19

climatological stress (e.g., temperature, drought) and shorter-term air pollutant stress (oxidants and metals ). Heavy metals of fine PM have been...speciation of the fine and coarse PM fractions will allow distinction between different PM sources such as wind blown soil dust, including dust...emitting 12% of the total PM2.5 mass (U.S. EPA, 2004b). Source apportionment modeling of PM2.5 mass concentrations from 24 Speciation Defense Coastal

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

DOE PAGES

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; ...

2017-05-19

Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.

Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

Quantification of Cation Sorption to Engineered Barrier Materials Under Extreme Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, Brian; Schlautman, Mark; Rao, Linfeng

The objective of this research is to examine mechanisms and thermodynamics of actinide sorption to engineered barrier materials (iron (oxyhydr)oxides and bentonite clay) for nuclear waste repositories under high temperature and high ionic strength conditions using a suite of macroscopic and microscopic techniques which will be coupled with interfacial reaction models. Gaining a mechanistic understanding of interfacial processes governing the sorption/sequestration of actinides at mineral-water interfaces is fundamental for the accurate prediction of actinide behavior in waste repositories. Although macroscale sorption data and various spectroscopic techniques have provided valuable information regarding speciation of actinides at solid-water interfaces, significant knowledge gapsmore » still exist with respect to sorption mechanisms and the ability to quantify sorption, particularly at high temperatures and ionic strengths. This objective is addressed through three major tasks: (1) influence of oxidation state on actinide sorption to iron oxides and clay minerals at elevated temperatures and ionic strengths; (2) calorimetric titrations of actinide-mineral suspensions; (3) evaluation of bentonite performance under repository conditions. The results of the work will include a qualitative conceptual model and a quantitative thermodynamic speciation model describing actinide partitioning to minerals and sediments, which is based upon a mechanistic understanding of specific sorption processes as determined from both micro-scale and macroscale experimental techniques. The speciation model will be a thermodynamic aqueous and surface complexation model of actinide interactions with mineral surfaces that is self-consistent with macroscopic batch sorption data, calorimetric and potentiometric titrations, X-ray absorption Spectroscopy (XAS, mainly Extended X-ray Absorption Fine Structure (EXAFS)), and electron microscopy analyses. The novelty of the proposed work lies largely in the unique system conditions which will be examined (i.e. elevated temperature and ionic strength) and the manner in which the surface complexation model will be developed in terms of specific surface species identified using XAS. These experiments will thus provide a fundamental understanding of the chemical and physical processes occurring at the solid-solution interface under expected repository conditions. Additionally, the focus on thermodynamic treatment of actinide ion interactions with minerals as proposed will provide information on the driving forces involved and contribute to the overall understanding of the high affinity many actinide ions have for oxide surfaces. The utility of this model will be demonstrated in this work through a series of advective and diffusive flow experiments.« less

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

NASA Astrophysics Data System (ADS)

Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel

2002-05-01

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Sulfur speciation in hydrous experimental glasses of varying oxidation state - Results from measured wavelength shifts of sulfur X-rays

NASA Technical Reports Server (NTRS)

Carroll, Michael R.; Rutherford, Malcolm J.

1988-01-01

The focusing geometry of an electron microprobe has been used to measure the wavelength shifts of sulfur X-rays from hydrous experimental melts synthesized at oxygen fugacities that range from near the iron-wustite buffer to the magnetite-hermatite buffer. It is found that the proportion of dissolved sulfur which is present as sulfate increases with increasing oxygen fugacity. It is noted that in natural melts that have equilibrated at or below fayalite-magnetite-quartz values of +1, sulfur is probably present mainly as S(2-).

POWER PLANT EVALUATION OF THE EFFECT OF SCR TECHNOLOGY ON MERCURY

EPA Science Inventory

The paper presents results of research on the impact that selective catalytic reduction (SCR) systems have on speciation and total emissions of mercury. Although SCR systems are designed to reduce nitrogen oxides (NOx), they may oxidize elemental mercury (Hg0) to Hg2+, which is m...

STUDY OF SPECIATION OF MERCURY UNDER SIMULATED SCR NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

The paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. It describes the results of bench-scale experiments conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures wit...

The importance of trace element speciation in biomedical science.

PubMed

Templeton, Douglas M

2003-04-01

According to IUPAC terminology, trace element speciation reflects differences in chemical composition at multiple levels from nuclear and electronic structure to macromolecular complexation. In the medical sciences, all levels of composition are important in various circumstances, and each can affect the bioavailability, distribution, physiological function, toxicity, diagnostic utility, and therapeutic potential of an element. Here we discuss, with specific examples, three biological principles in the intimate relation between speciation and biological behavior: i) the kinetics of interconversion of species determines distribution within the organism, ii) speciation governs transport across various biological barriers, and iii) speciation can limit potentially undesirable interactions between physiologically essential elements. We will also describe differences in the speciation of iron in states of iron overload, to illustrate how speciation analysis can provide insight into cellular processes in human disease.

The influence of metal speciation in combustion waste on the efficiency of Cu, Pb, Zn, Cd, Ni and Cr bioleaching in a mixed culture of sulfur-oxidizing and biosurfactant-producing bacteria.

PubMed

Karwowska, Ewa; Wojtkowska, Małgorzata; Andrzejewska, Dorota

2015-12-15

Metal leachability from ash and combustion slag is related to the physico-chemical properties, including their speciation in the waste. Metals speciation is an important factor that influences the efficiency of metal bioleaching from combustion wastes in a mixed culture of acidophilic and biosurfactant-producing bacteria. It was observed that individual metals tended to occur in different fractions, which reflects their susceptibility to bioleaching. Cr and Ni were readily removed from wastes when present with a high fraction bound to carbonates. Cd and Pb where not effectively bioleached when present in high amounts in a fraction bound to organic matter. The best bioleaching results were obtained for power plant slag, which had a high metal content in the exchangeable, bound to carbonates and bound to Fe and Mg oxides fractions- the metal recovery percentage for Zn, Cu and Ni from this waste exceeded 90%. Copyright © 2015 Elsevier B.V. All rights reserved.

Speciation of iron in ambient aerosol and cloudwater

NASA Astrophysics Data System (ADS)

Siefert, Ronald Lyn

1997-03-01

Atmospheric iron (Fe) is thought to play an important role in cloudwater chemistry (e.g., S(IV) oxidation, oxidant production, etc.), and is also an important source of Fe to certain regions of the world's oceans where Fe is believed to be a rate-limiting nutrient for primary productivity. This thesis focuses on understanding the chemistry, speciation and abundance of Fe in cloudwater and aerosol in the troposphere, through observations of Fe speciation in the cloudwater and aerosol samples collected over the continental United States and the Arabian Sea. Different chemical species of atmospheric Fe were measured in aerosol and cloudwater samples to help assess the role of Fe in cloudwater chemistry. Chapter 2 presents a set of experiments which used ambient aerosol samples suspended in aqueous solution and then irradiated with uv-light to simulate cloudwater conditions. These experiments found Fe to be a critical component for the production of H2O2. Chapter 3 discusses the development and application of a novel photochemical extraction method for the determination of photochemically-available Fe in ambient aerosol samples. Photochemically-available Fe ranged from <4 ng m-3 to 308 ng m-3, and accounted for 2.8% to 100% of the total Fe in aerosol samples collected in California and New York. Calculations based on the results of these experiments predicted that redox reactions of Fe in cloudwater could be an important in situ source of oxidants (ċOH, HO2ċ/O2/cdot/sb- ). Chapter 4 presents results of several field studies which measured the redox states of Fe and other transition metals (Mn, Cu and Cr) in cloudwater. These measurements were then used in thermodynamic models which predicted Fe(III) to be either as Fe(III)-hydroxy species or Fe(III)-oxalate species. However, an unidentified strong chelating ligand with Fe(III) was also suggested by the thermodynamic model results. Chapter 5 presents results of a field study conducted on the Arabian Sea. Total atmospheric labile-Fe(II) ranged between <0.09 ng m-3 to 7.5 ng m-3 during the inter-monsoon period, and was consistently below the detection limit during the southwest-monsoon period. The labile-Fe(II) measured during the inter-monsoon period was predominantly found in the fine fraction of the aerosol. Principal component analysis revealed a significant source of Fe and Mn which was not associated with the main aeolian dust component.

Phosphorus solubility of agricultural soils: a surface charge and phosphorus-31 NMR speciation study

USDA-ARS?s Scientific Manuscript database

We investigated ten soils from six states in United States to determine the relationship between potentiometric titration derived soil surface charge and Phosphorus-31 (P) nuclear magnetic resonance (NMR) speciation with the concentration of water-extractable P (WEP). The surface charge value at the...

XANES Spectroscopic Analysis of Phosphorus Speciation in Alum-Amended Poultry Litter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seiter,J.; Staats-Borda, K.; Ginder-Vogel, M.

2008-01-01

Aluminum sulfate (alum; Al2(SO4)3{center_dot}14H2O) is used as a chemical treatment of poultry litter to reduce the solubility and release of phosphate, thereby minimizing the impacts on adjacent aquatic ecosystems when poultry litter is land applied as a crop fertilizer. The objective of this study was to determine, through the use of X-ray absorption near edge structure (XANES) spectroscopy and sequential extraction, how alum amendments alter P distribution and solid-state speciation within the poultry litter system. Our results indicate that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. Analysis shows that NaOH-extracted Pmore » in alum amended litters is predominantly organic ({approx}80%), whereas in the control samples, >60% of NaOH-extracted P was inorganic P. Linear least squares fitting (LLSF) analysis of spectra collected of sequentially extracted litters showed that the P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum-amended poultry litter. When determining land application rates of poultry litter, all of these compounds must be considered, especially organic P. Results of the sequential extractions in conjunction with LLSF suggest that no P species is completely removed by a single extractant. Rather, there is a continuum of removal as extractant strength increases. Overall, alum-amended litters exhibited higher proportions of Al-bound P species and phytic acid, whereas untreated samples contained Ca-P minerals and organic P compounds. This study provides in situ information about P speciation in the poultry litter solid and about P availability in alum- and non-alum-treated poultry litter that will dictate P losses to ground and surface water systems.« less

Characterization of uranium redox state in organic-rich Eocene sediments.

PubMed

Cumberland, Susan A; Etschmann, Barbara; Brugger, Joël; Douglas, Grant; Evans, Katy; Fisher, Louise; Kappen, Peter; Moreau, John W

2018-03-01

The presence of organic matter (OM) has a profound impact on uranium (U) redox cycling, either limiting or promoting the mobility of U via binding, reduction, or complexation. To understand the interactions between OM and U, we characterised U oxidation state and speciation in nine OM-rich sediment cores (18 samples), plus a lignite sample from the Mulga Rock polymetallic deposit in Western Australia. Uranium was unevenly dispersed within the analysed samples with 84% of the total U occurring in samples containing >21 wt % OM. Analyses of U speciation, including x-ray absorption spectroscopy and bicarbonate extractions, revealed that U existed predominately (∼71%) as U(VI), despite the low pH (4.5) and nominally reducing conditions within the sediments. Furthermore, low extractability by water, but high extractability by a bi-carbonate solution, indicated a strong association of U with particulate OM. The unexpectedly high proportion of U(VI) relative to U(IV) within the OM-rich sediments implies that OM itself does not readily reduce U, and the reduction of U is not a requirement for immobilizing uranium in OM-rich deposits. The fact that OM can play a significant role in limiting the mobility and reduction of U(VI) in sediments is important for both U-mining and remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Immobilization of selenate by iron in aqueous solution under anoxic conditions and the influence of uranyl

NASA Astrophysics Data System (ADS)

Puranen, Anders; Jonsson, Mats; Dähn, Rainer; Cui, Daqing

2009-08-01

In proposed high level radioactive waste repositories a large part of the spent nuclear fuel (SNF) canisters are commonly composed of iron. Selenium is present in spent nuclear fuel as a long lived fission product. This study investigates the influence of iron on the uptake of dissolved selenium in the form of selenate and the effect of the presence of dissolved uranyl on the above interaction of selenate. The iron oxide, and selenium speciation on the surfaces was investigated by Raman spectroscopy. X-ray Absorption Spectroscopy was used to determine the oxidation state of the selenium and uranium on the surfaces. Under the simulated groundwater conditions (10 mM NaCl, 2 mM NaHCO 3, <0.1 ppm O 2) the immobilized selenate was found to be reduced to oxidation states close to zero or lower and uranyl was found to be largely reduced to U(IV). The near simultaneous reduction of uranyl was found to greatly enhance the rate of selenate reduction. These findings suggest that the presence of uranyl being reduced by an iron surface could substantially enhance the rate of reduction of selenate under anoxic conditions relevant for a repository.

Speciation of Mg in biogenic calcium carbonates

NASA Astrophysics Data System (ADS)

Farges, F.; Meibom, A.; Flank, A.-M.; Lagarde, P.; Janousch, M.; Stolarski, J.

2009-11-01

A selection of marine biominerals, mostly aragonitic coral skeletons were probed at the Mg K-edge by XANES spectroscopy coupled to μXRF methods and compared to an extensive set of relevant model compounds (silicates, carbonates, oxides and organic). Extensive methodologies are required to better describe the speciation of Mg in those minerals. A combination of ab-initio XANES calculations for defective clusters around Mg in aragonite together with wavelets analyzes of the XANES region are required to robustly interpret the spectra. When using those methodologies, the speciation of Mg ranges from a magnesite-type environment in some scleractinian corals to an organic-type environment. In all environments, the Mg-domains probed appear to be less than 1 nm in size.

Effect of oxy-combustion flue gas on mercury oxidation.

PubMed

Fernández-Miranda, Nuria; Lopez-Anton, M Antonia; Díaz-Somoano, Mercedes; Martínez-Tarazona, M Rosa

2014-06-17

This study evaluates the effect of the gases present in a typical oxy-coal combustion atmosphere on mercury speciation and compares it with the mercury speciation produced in conventional air combustion atmospheres. The work was performed at laboratory scale at 150 °C. It was found that the minor constituents (SO2, NOx, and HCl) significantly modify the percentages of Hg(2+) in the gas. The influence of these species on mercury oxidation was demostrated when they were tested individually and also when they were blended in different gas compositions, although the effect was different to the sum of their individual effects. Of the minor constituents, NOx were the main species involved in oxidation of mercury. Moreover, it was found that a large concentration of H2O vapor also plays an important role in mercury oxidation. Around 50% of the total mercury was oxidized in atmospheres with H2O vapor concentrations typical of oxy-combustion conditions. When the atmospheres have similar concentrations of SO2, NO, NO2, HCl, and H2O, the proportion of Hg(0)/Hg(2+) is similar regardless of whether CO2 (oxy-fuel combustion) or N2 (air combustion) are the main components of the gas.

Arsenic and chromium speciation in an urban contaminated soil.

PubMed

Landrot, Gautier; Tappero, Ryan; Webb, Samuel M; Sparks, Donald L

2012-08-01

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)⋅2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil. Copyright © 2012 Elsevier Ltd. All rights reserved.

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

PubMed

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

Kinetic concepts to quantify the role of oxidants and photooxidants in natural waters and water treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoigne, J.

1995-12-31

Research performed during the last two decades has led to a significant evolution of reaction kinetic concepts to estimate the role of reactive oxidants and photooxidants in natural waters and for water treatment. Although many reaction-rate data for oxidants such as OH and HO{sub 2}/O{sub 2}{sup -} radicals, O{sub 2} and O{sub 3} or ClO{sub 2} had been compiled before, these were rather selected to elucidate other areas of research and applications. Their critical applications for describing reactions of interest for aqueous chemistry has then required to extend the compilations of rate data: (1) to include more reactions of relevancemore » in aqueous media, (2) to critically account for the aqueous speciations, (3) to experimentally characterise the environmental factors controlling the steady-state concentration of different oxidants, (4) to formulate models useful for computing predictions and allowing for critical experimental tests, and (5) to allow for a unified concept for teaching environmental chemistry that better approaches the concepts of classical chemistry.« less

Bromide's effect on DBP formation, speciation, and control; Part 1: Ozonation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukairy, H.M.; Summers, R.S.; Miltner, R.J.

1994-06-01

The effect of variable ozone dosage and bromide concentration on the formation of organic disinfection by-products (DBPs) and bromate were evaluated. Low ozone dosages resulted in oxidation of organic precursors, yielding decreases in the formation potential for total trihalomethanes (THMs), six haloacetic acids (HAAs), and total organic halide (TOX). Increasing the ozone dosage oxidized bromide to bromate, decreasing the bromide for incorporation into DBPs. Bromate concentrations were linearly correlated with ozone residuals. Changes in the bromine incorporation factors n and n[prime] reflected differences in the resulting speciation of THMs and HAAs, respectively. Because TOX measurements based on chloride equivalence maymore » underestimate the halogenated DBP yield for high-bromide waters, a procedure is described whereby bromide and bromate concentrations were used to correct the TOX measurement.« less

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.

Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the firstmore » generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentially enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant and Aerosol Study (SOAS). We compare these speciated measurements to total unspeciated particulate organic nitrate measured by three independent methods, and analyze using a zero-dimensional box model the diel cycles of individual components to elucidate differential source and sink terms. Biogenic volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes appear to dominate the ON sources during SOAS. We show that the molecular compositions that dominate the particle-phase are significantly more oxygenated than the most abundant gas-phase counterparts, consistent with volatility and solubility driven partitioning requirements. However, the detailed mechanisms by which most of these ON arise are not yet clear. These speciated measurements put a strong constraint on the extent to which ON directly contribute to SOA in regions with high biogenic hydrocarbon emissions, and illustrate that the fate of particulate ON can have significant implications for SOA and the reactive nitrogen budget.« less

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

DOE PAGES

Lee, Ben H.; Mohr, Claudia; Lopez-Hilfiker, Felipe D.; ...

2016-01-25

Organic nitrates (ON = RONO2 + RO2NO2) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NOx=NO+NO2). ON formed from isoprene oxidation alone are responsible for the export of 8 to 30% of anthropogenic NOx out of the U.S. continental boundary layer [Horowitz et al., 1998; Liang et al., 1998]. Regional NOx budgets and tropospheric ozone (O3) production, are therefore particularly sensitive to uncertainties in the yields and fates of ON [Beaver et al., 2012; Browne et al., 2013]. The yields implemented in modeling studies are determined from laboratory experiments in which only a few of the firstmore » generation gaseous ON or the total gas and particle-phase ON have been quantified [Perring et al., 2013 and references therein], while production of highly functionalized ON capable of strongly partitioning to the particle-phase have been inferred [Farmer et al., 2010; Ng et al., 2007; Nguyen et al., 2011; Perraud et al., 2012; Rollins et al., 2012], or directly measured [Ehn et al., 2014]. Addition of a nitrate (–ONO2) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5 to 3 orders of magnitude [e.g. Capouet and Muller, 2006]. Thus, organic nitrate formation can potentially enhance particle-phase partitioning of hydrocarbons in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) formation [Ng et al., 2007]. There has, however, been no high time-resolved measurements of speciated ON in the particle-phase. We utilize a newly developed high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adduct ionization [B H Lee et al., 2014a] with a filter inlet for gases and aerosols (FIGAERO) [Lopez-Hilfiker et al., 2014] that allows alternating in situ measurement of the molecular composition of gas and particle phases. We present observations of speciated ON in the particle-phase obtained during the 2013 Southern Oxidant and Aerosol Study (SOAS). We compare these speciated measurements to total unspeciated particulate organic nitrate measured by three independent methods, and analyze using a zero-dimensional box model the diel cycles of individual components to elucidate differential source and sink terms. Biogenic volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes appear to dominate the ON sources during SOAS. We show that the molecular compositions that dominate the particle-phase are significantly more oxygenated than the most abundant gas-phase counterparts, consistent with volatility and solubility driven partitioning requirements. However, the detailed mechanisms by which most of these ON arise are not yet clear. These speciated measurements put a strong constraint on the extent to which ON directly contribute to SOA in regions with high biogenic hydrocarbon emissions, and illustrate that the fate of particulate ON can have significant implications for SOA and the reactive nitrogen budget.« less

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2012-09-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2013-01-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Phosphorus speciation by coupled HPLC-ICPMS: low level determination of reduced phosphorus in natural materials

NASA Astrophysics Data System (ADS)

Atlas, Zachary; Pasek, Matthew; Sampson, Jacqueline

2015-04-01

Phosphorus is a geologically important minor element in the Earth's crust commonly found as relatively insoluble apatite. This constraint causes phosphorus to be a key limiting nutrient in biologic processes. Despite this, phosphorus plays a direct role in the formation of DNA, RNA and other cellular materials. Recent works suggest that since reduced phosphorus is considerably more soluble than oxidized phosphorus that it was integrally involved in the development of life on the early Earth and may continue to play a role in biologic productivity to this day. This work examines a new method for quantification and identification of reduced phosphorus as well as applications to the speciation of organo-phosphates separated by coupled HPLC - ICP-MS. We show that reduced phosphorus species (P1+, P3+ and P5+) are cleanly separated in the HPLC and coupled with the ICPMS reaction cell, using oxygen as a reaction gas to effectively convert elemental P to P-O. Analysis at M/Z= 47 producing lower background and flatter baseline chromatography than analyses performed at M/Z = 31. Results suggest very low detection limits (0.05 μM) for P species analyzed as P-O. Additionally we show that this technique has potential to speciate at least 5 other forms of phosphorus compounds. We verified the efficacy of method on numerous materials including leached Archean rocks, suburban retention pond waters, blood and urine samples and most samples show small but detectible levels of reduced phosphorus and or organo-phaospates. This finding in nearly all substances analyzed supports the assumption that the redox processing of phosphorus has played a significant role throughout the history of the Earth and it's presence in the present environment is nearly ubiquitous with the reduced oxidation state phosphorus compounds, phosphite and hypophosphite, potentially acting as significant constituents in the anaerobic environment.

Quantitative traits and diversification.

PubMed

FitzJohn, Richard G

2010-12-01

Quantitative traits have long been hypothesized to affect speciation and extinction rates. For example, smaller body size or increased specialization may be associated with increased rates of diversification. Here, I present a phylogenetic likelihood-based method (quantitative state speciation and extinction [QuaSSE]) that can be used to test such hypotheses using extant character distributions. This approach assumes that diversification follows a birth-death process where speciation and extinction rates may vary with one or more traits that evolve under a diffusion model. Speciation and extinction rates may be arbitrary functions of the character state, allowing much flexibility in testing models of trait-dependent diversification. I test the approach using simulated phylogenies and show that a known relationship between speciation and a quantitative character could be recovered in up to 80% of the cases on large trees (500 species). Consistent with other approaches, detecting shifts in diversification due to differences in extinction rates was harder than when due to differences in speciation rates. Finally, I demonstrate the application of QuaSSE to investigate the correlation between body size and diversification in primates, concluding that clade-specific differences in diversification may be more important than size-dependent diversification in shaping the patterns of diversity within this group.

Speciation and leaching of trace metal contaminants from e-waste contaminated soils.

PubMed

Cui, Jin-Li; Luo, Chun-Ling; Tang, Chloe Wing-Yee; Chan, Ting-Shan; Li, Xiang-Dong

2017-05-05

Primitive electrical and electronic waste (e-waste) recycling activities have caused serious environmental problems. However, little is known about the speciation and leaching behaviors of metal contaminants at e-waste contaminated sites. This study investigated trace metal speciation/mobilization from e-waste polluted soil through column leaching experiments involving irrigation with rainwater for almost 2.5 years. Over the experimental period, Cu and Zn levels in the porewater were 0.14±0.08mg/L, and 0.16±0.08mg/L, respectively, increasing to 0.33±0.16mg/L, and 0.69±0.28mg/L with plant growth. The amounts of Cu, Zn, and Pb released in surface soil (0-2cm) contributed 43.8%, 22.5%, and 13.8%, respectively, to the original levels. The released Cu and Zn were primarily caused by the mobilization of the carbonate species of metals, including Cu(OH) 2 , CuCO 3 , and Zn 5 (CO 3 ) 2 (OH) 6 , and amorphous Fe/Mn oxides associated fractions characterized by sequential extraction coupling with X-ray absorption spectroscopy. During the experiments, trace metals were not detected in the effluent, and the re-sequestration of trace metals was mainly attributed to the adsorption on the abundant Fe/Mn oxides in the sub-layer soil. This study quantitatively elucidated the molecular speciation of Cu and Zn in e-waste contaminated soil during the column leaching process. Copyright © 2017 Elsevier B.V. All rights reserved.

Arsenic Speciation and Cadmium Determination in Tobacco Leaves, Ash and Smoke.

PubMed

Iwai, Takahiro; Chiba, Koichi; Narukawa, Tomohiro

2016-01-01

The concentrations of arsenic (As) and cadmium (Cd) in the tobacco leaves, ash and smoke of 10 kinds of cigarettes collected from different countries worldwide were determined by ICP-MS after microwave-assisted digestion. Total As and Cd concentrations in the tobacco leaves ranged from 0.20 to 0.63 and 1.8 to 9.9 mg kg(-1), respectively. By the speciation analysis of As in tobacco leaves and ash by HPLC-ICP-MS following acid extraction, arsenite [As(III)] and arsenate [As(V)] were determined and trace amounts of monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA) and some unidentified As species were also found. Arsenic speciation for smoke absorbed in an aqueous solution was carried out. The sum of the As species in tobacco leaves, ash and smoke was in good agreement with the result of total As determination in each sample, and the recoveries of speciation were 100 ± 10%. The distributions and the behaviors of As species were clarified.

MERCURY SPECIATION IN COMBUSTION SYSTEMS: STUDIES WITH SIMULATED FLUE GASES AND MODEL FLY ASHES

EPA Science Inventory

The paper gives results of a bench-scale study of the effects of flue gas and fly ash parameters on the oxidation of elemental mercury in simulated flue gases containing hydrogen chloride (HCl), nitric oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and water vapor (H2O...

Microbiological Transformations of Radionuclides in the Subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, Matthew J.; Beliaev, Alex S.; Fredrickson, Jim K.

2010-01-04

Microorganisms are ubiquitous in subsurface environments although their populations sizes and metabolic activities can vary considerably depending on energy and nutrient inputs. As a result of their metabolic activities and the chemical properties of their cell surfaces and the exopolymers they produce, microorganisms can directly or indirectly facilitate the biotransformation of radionuclides, thus altering their solubility and overall fate and transport in the environment. Although biosorption to cell surfaces and exopolymers can be an important factor modifying the solubility of some radionuclides under specific conditions, oxidation state is often considered the single most important factor controlling their speciation and, therefore,more » environmental behavior.« less

Uptake of elements from seawater by ferromanganese crusts: Solid-phase associations and seawater speciation

USGS Publications Warehouse

Koschinsky, A.; Hein, J.R.

2003-01-01

Marine Fe-Mn oxyhydroxide crusts form by precipitation of dissolved components from seawater. Three hydrogenetic crust samples (one phosphatized) and two hydrothermal Mn-oxide samples were subjected to a sequential-leaching procedure in order to determine the host phases of 40 elements. Those host-phase associations are discussed with respect to element speciation in seawater. The partitioning of elements between the two major phases, Mn oxide and Fe oxyhydroxide, can in a first-order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater, as has been proposed in earlier models. Free and weakly complexed cations, such as alkali and alkaline earth metals, Mn, Co, Ni, Zn, T1(I), and partly Y, are sorbed preferentially on the negatively charged surface of the MnO2 in hydrogenetic crusts. The driving force is a strong coulombic interaction. All neutral or negatively charged chloro (Cd, Hg, T1), carbonate (Cu, Y, Pb, and U), and hydroxide (Be, Sc, Ti, Fe, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, Bi, Th, and T1(III)) complexes and oxyanions (V, Cr, As, Se, Mo, and W) bind to the slightly positively charged surface of the amorphous FeOOH phase. While coulombic interaction can explain the sorption of the negatively charged species, the binding of neutral species is based on specific chemical interaction. Organic complexation of elements in deep-ocean water seems to be at most of minor importance. Surface oxidation can explain some strong metal associations, e.g. of Co and T1 with the MnO2 and Te with the FeOOH. Sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface. Differences in the associations of some metals between the non-phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico-chemical environments of formation and speciations in oxic seawater vs. less-oxic fluids, especially for the redox-sensitive metals such as Mo and V. These environmental-related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth. ?? 2003 Elsevier Science B.V. All rights reserved.

Source and distribution of sedimentary thallium in the Bohai Sea: Implications for hydrodynamic forces and anthropogenic impact

NASA Astrophysics Data System (ADS)

Hu, Ningjing; Liu, Jihua; Shi, Xuefa

2015-04-01

Source and distribution of sedimentary thallium in the Bohai Sea: Implications for hydrodynamic forces and anthropogenic impact Hu Ningjing, Liu Jihua, Shi Xuefa First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China Thallium (Tl), a non-essential and highly toxic trace metal, is listed as priority toxic pollutant by the United States Environmental Protection Agency (USEPA) (Keith and Telliard, 1979). However, its geochemical cycling in aquatic environment has received far less attention than that of many other trace metals. This has been attributed to relatively little commercial interest in Tl and, until recently, problems inherent in its detection at environmental concentrations (Meeravali and Jiang, 2008). In this study, we investigated the sources, distribution and fate of Tl in surface sediments of the Bohai Sea (BS), China, based on the datasets of total Tl and chemical speciation of Tl of 408 surface sediment samples in the total entire BS. The enrichment factors and chemical speciation of Tl indicated that Tl in BS was dominated by natural Tl, although anthropogenic Tl contamination was observed in the Liuguhe River mouth; the mud deposits are the sinks of Tl and the regional currents and tide systems play a key role on the accumulation of Tl in BS. The distribution of Tl consistent with that of MnO and Fe2O3 as well as the level of Fe-Mn fraction is relatively high, indicating MnO and Fe2O3 influence the geochemical behaviors of Tl in the BS. Although the positive correlation between Tl and TOC is observed for the samples in the BS, however, level of Tl in oxidizable faction could be neglected, suggesting TOC might not be a major factor affecting the concentration of Tl in BS. The low proportion of Tl in the non-residual fraction dominated by the Fe-Mn oxides suggested that the labile Tl was controlled by the Fe-Mn oxides and Tl has a low bioavailability and a minor potential threat to biota in BS. Acknowledgements: this work was jointly supported by National Natural Science Foundation of China (Grant Nos.41076032, 41276052 and 41376073) and the State Oceanic Administration, China (Grant No. 201105003). References Keith, L.H., Telliard, W.A., 1979. Priority pollutants-A perspective view. Environmental Science and Technology 13, 416-423. Meeravali, N.M., Jiang, S.-J., 2008. Ultra-trace speciation analysis of thallium in environmental water samples by inductively coupled plasma mass spectrometry after a novel sequential mixed-micelle cloud point extraction. Journal of Analytical Atomic Spectrometry 23, 555-560.

The phosphorus speciations in the sediments up- and down-stream of cascade dams along the middle Lancang River.

PubMed

Liu, Qi; Liu, Shiliang; Zhao, Haidi; Deng, Li; Wang, Cong; Zhao, Qinghe; Dong, Shikui

2015-02-01

We detected the longitudinal variability of phosphorus speciations and its relation to metals and grain size distribution of sediments in three cascade canyon reservoirs (Xiaowan, Manwan and Dachaoshan) along Lancang River, China. Five phosphorus speciations including loosely bound P (ex-P), reductant soluble P (BD-P), metal oxide-bound P (NaOH-P) calcium-bound P (HCl-P) and residual-P were extracted and quantified. Results showed that in Manwan Reservoir HCl-P accounted for the largest part of total phosphorus (TP) (49.69%), while in Xiaowan and Dachaoshan reservoirs, NaOH-P was the most abundant speciation which accounted for 57.21% and 55.19% of total phosphorus respectively. Higher contents of bio-available phosphorus in Xiaowan and Dachaoshan reservoirs suggested a high rate of P releasing from sediments. Results also showed ex-P and HCl-P had positive correlation with Ca. Total phosphorus was positively correlated with Fe. The silt/clay contents of the sediments had close relationship with ex-P (r=0.413, p<0.05), NaOH-P (r=0.428, p<0.05) and BAP (r=0.458, p<0.05). The concentration of Ca, Mn and silt/clay speciation in the sediments explained 40%, 10% and 4% of the spatial variation of phosphorus speciations, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions.

PubMed

Lee, Chun W; Srivastava, Ravi K; Ghorishi, S Behrooz; Hastings, Thomas W; Stevens, Frank M

2004-12-01

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.

Investigation of arsenic species in tailings and windblown dust from a gold mining area.

PubMed

Ono, F B; Tappero, R; Sparks, D; Guilherme, L R G

2016-01-01

Research has shown the presence of high levels of arsenic (up to 2666 mg As kg(-1)) in tailings from a gold mining area of Brazil. This is an important point of attention, generating concerns about impacts on human health. Yet, a recent study showed that As bioaccessibility in the same area was very low (<4.4%). Thus, determination of the direct solid-phase speciation of As in the mine tailings and windblown dust is needed to explain this low bioaccessibility. Mine samples were collected from four subareas and windblown dust from eight sites. Synchrotron-based bulk-X-ray absorption near-edge structure (bulk-XANES) spectroscopy, micro-X-ray absorption near-edge structure (μ-XANES), and μ-X-ray fluorescence (μ-SXRF) spectroscopy were applied to determine As speciation. Bulk-XANES spectra indicated that As occurs as the As(V) oxidation state. Micro-XANES and μ-SXRF analyses revealed that As was also present as arsenopyrite (FeAsS) and its weathering products, but mostly it was As(V) as poorly crystalline ferric arsenate. This supports the findings of low bioaccessible As and highlights the importance of Fe oxides in immobilizing As in the terrestrial environment. All air particulate samples exhibited As-rich particles (up to 313 mg As kg(-1)). The air particulates exhibited solid-phase As species very similar to those found in the mine samples, which indicates that As in the windblown dust is not easily available.

Surface reactions kinetics between nanocrystalline magnetite and uranyl.

PubMed

Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel

2003-05-01

Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution.

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

Kinetic model to explain the effect of ocean warming and acidification on the Fe(II) oxidation rate in oligotrophic and eutrophic natural waters

NASA Astrophysics Data System (ADS)

González-Dávila, M.; Samperio-Ramos, G.; Santana-Casiano, J. M.; Gonzallez, A. G.; Pérez-Almeida, N.

2016-12-01

The speciation of inorganic Fe(II) as a function of the pH and temperature have been modeled in order to elucidate the inorganic Fe(II) redox behavior over a wide range of scenarios of acidification and global warming of the upper ocean, as well as, changes due to natural ambient fluctuations of pH and temperature. In addition, a kinetic modeling approach has been carried out to elucidate the fractional contribution of most kinetically active Fe(II) species to the overall oxidation rate to improve our future and present knowledge with respect to redox iron chemistry in the marine systems. The kinetic model considers the interactions of Fe(II) with the major ions in seawater, including phosphate and silicate and the competition with copper with the ROS. The model has been applied to the experimental results in order to describe the effect of temperature and pH in the speciation of Fe(II) and to compute the fractional contribution of each Fe(II)-specie to the overall oxidation rate. The oxidation rates (kapp) of nanomolar levels of Fe(II) have been studied in seawater enriched with nutrients (SWEN) in air saturated conditions. The nutrient effect (nitrate, phosphate and silicate), on the oxidation of Fe(II), has been evaluated as a function of pH (7.2-8.2), temperature (5-35 ºC) and salinity (10-37.09). The oxidation of Fe(II) was faster in the presence of nutrient with the change in the Fe(II) oxidation rates (Δlogkapp) more intensive at higher temperatures over the entire pH range studied. From the model it can be observed that the inorganic speciation of Fe(II) is controlled largely by pH, either in SW or in SWEN. A greater presence of Fe-nutrient reactive species (FeH3SiO4+ and FePO4-) in SWEN at higher temperatures explained the changes in the oxidation process. The individual oxidation rates by oxygen, for the Fe(II) most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3(OH)-, FeCO3, Fe(CO3)22-, FeH3SiO3+, FePO4-), were fitted as a function of the temperature.

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation.

PubMed

Melin, Victoria; Henríquez, Adolfo; Freer, Juanita; Contreras, David

2015-03-01

Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

Theoretical Modeling of 99 Tc NMR Chemical Shifts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hall, Gabriel B.; Andersen, Amity; Washton, Nancy M.

Technetium (Tc) displays a rich chemistry due to the wide range of oxidation states (from -I to +VII) and ability to form coordination compounds. Determination of Tc speciation in complex mixtures is a major challenge, and 99Tc NMR spec-troscopy is widely used to probe chemical environments of Tc in odd oxidation states. However interpretation of the 99Tc NMR data is hindered by the lack of reference compounds. DFT computations can help fill this gap, but to date few com-putational studies have focused on 99Tc NMR of compounds and complexes. This work systematically evaluates the inclu-sion small percentages of Hartree-Fock exchangemore » correlation and relativistic effects in DFT computations to support in-terpretation of the 99Tc NMR spectra. Hybrid functionals are found to perform better than their pure GGA counterparts, and non-relativistic calculations have been found to generally show a lower mean absolute deviation from experiment. Overall non-relativistic PBE0 and B3PW91 calculations are found to most accurately predict 99Tc NMR chemical shifts.« less

Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.

2014-06-02

The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction ofmore » S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.« less

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

PubMed

Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

2014-02-01

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

Speciation and weathering of selenium in upper cretaceous chalk and shale from South Dakota and Wyoming, USA

NASA Astrophysics Data System (ADS)

Kulp, Thomas R.; Pratt, Lisa M.

2004-09-01

In geologic materials, petroleum, and the environment, selenium occurs in various oxidation states (VI, IV, 0, -II), mineralized forms, and organo-Se complexes. Each of these forms is characterized by specific chemical and biochemical properties that control the element's solubility, toxicity, and environmental behavior. The organic rich chalks and shales of the Upper Cretaceous Niobrara Formation and the Pierre Shale in South Dakota and Wyoming are bentoniferous stratigraphic intervals characterized by anomalously high concentrations of naturally occurring Se. Numerous environmental problems have been associated with Se derived from these geological units, including the development of seleniferous soils and vegetation that are toxic to livestock and the contamination of drinking water supplies by Se mobilized in groundwater. This study describes a sequential extraction protocol followed by speciation treatments and quantitative analysis by Hydride Generation-Atomic Absorption Spectroscopy. This protocol was utilized to investigate the geochemical forms and the oxidation states in which Se occurs in these geologic units. Organic Se and di-selenide minerals are the predominant forms of Se present in the chalks, shales, and bentonites, but distinctive variations in these forms were observed between different sample types. Chalks contain significantly greater proportions of Se in the form of di-selenide minerals (including Se associated with pyrite) than the shales where base-soluble, humic, organo-Se complexes are more prevalent. A comparison between unweathered samples collected from lithologic drill cores and weathered samples collected from outcrop suggest that the humic, organic-Se compounds in shale are formed during oxidative weathering and that Se oxidized by weathering is more likely to be retained by shale than by chalk. Selenium enrichment in bentonites is inferred to result from secondary processes including the adsorption of Se mobilized by groundwater from surrounding organic rich sediments to clay mineral and iron hydroxide surfaces, as well as microbial reduction of Se within the bentonitic intervals. Distinct differences are inferred for the biogeochemical pathways that affected sedimentary Se sequestration during periods of chalk accumulation compared to shale deposition in the Cretaceous seaway. Mineralogy of sediment and the nature of the organic matter associated with each of these rock types have important implications for the environmental chemistry and release of Se to the environment during weathering.

Arsenic and antimony geochemistry of mine wastes, associated waters and sediments at the Giant Mine, Yellowknife, Northwest Territories, Canada

USGS Publications Warehouse

Fawcett, Skya E.; Jamieson, Heather E.; Nordstrom, D. Kirk; McCleskey, R. Blaine

2015-01-01

Elevated levels of arsenic (As) and antimony (Sb) in water and sediments are legacy residues found downstream from gold-mining activities at the Giant Mine in Yellowknife, Northwest Territories (NWT), Canada. To track the transport and fate of As and Sb, samples of mine-waste from the mill, and surface water, sediment, pore-water, and vegetation downstream of the mine were collected. Mine waste, pore-water, and sediment samples were analyzed for bulk chemistry, and aqueous and solid-state speciation. Sediment and vegetation chemistry were evaluated using scanning electron microscope imaging, synchrotron-based element mapping and electron microprobe analysis. The distributions of As and Sb in sediments were similar, yet their distributions in the corresponding pore-waters were mostly dissimilar, and the mobility of As was greater than that of Sb. Competition for sorption sites is the most likely cause of elevated Sb concentrations in relatively oxidized pore-water and surface water. The aqueous and solid-state speciation of As and Sb also differed. In pore-water, As(V) dominated in oxidizing environments and As(III) in reducing environments. In contrast, the Sb(V) species dominated in all but one pore-water sample, even under reducing conditions. Antimony(III) appears to preferentially precipitate or adsorb onto sulfides as evidenced by the prevalence of an Sb(III)-S secondary solid-phase and the lack of Sb(III)(aq) in the deeper zones. The As(V)–O solid phase became depleted with depth below the sediment–water interface, and the Sb(V)–O phase persisted under relatively reducing conditions. In the surficial zone at a site populated by Equisetum fluviatile (common horsetail), As and Sb were associated with organic material and appeared mobile in the root zone. In the zone below active plant growth, As and Sb were associated primarily with inorganic phases suggesting a release and reprecipitation of these elements upon plant death. The co-existence of reduced and oxidized As and Sb species, instability of some phases under changing redox conditions, and plant uptake and release pose challenges for remediation efforts at the mine.

Impact of ozonation on naphthenic acids speciation and toxicity of oil sands process-affected water to Vibrio fischeri and mammalian immune system.

PubMed

Wang, Nan; Chelme-Ayala, Pamela; Perez-Estrada, Leonidas; Garcia-Garcia, Erick; Pun, Jonathan; Martin, Jonathan W; Belosevic, Miodrag; Gamal El-Din, Mohamed

2013-06-18

Oil sands process-affected water (OSPW) is the water contained in tailings impoundment structures in oil sands operations. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. In this study, ozonation followed by biodegradation was used to remediate OSPW. The impacts of the ozone process evolution on the naphthenic acids (NAs) speciation and acute toxicity were evaluated. Ion-mobility spectrometry (IMS) was used to preliminarily separate isomeric and homologous species. The results showed limited effects of the ozone reactor size on the treatment performance in terms of contaminant removal. In terms of NAs speciation, high reactivity of NAs with higher number of carbons and rings was only observed in a region of high reactivity (i.e., utilized ozone dose lower than 50 mg/L). It was also found that nearly 0.5 mg/L total NAs was oxidized per mg/L of utilized ozone dose, at utilized ozone doses lower than 50 mg/L. IMS showed that ozonation was able to degrade NAs, oxidized NAs, and sulfur/nitrogenated NAs. Complete removal of toxicity toward Vibrio fischeri was achieved after ozonation followed by 28-day biodegradation period. In vitro and in vivo assays indicated that ozonation reduced the OSPW toxicity to mice.

Exploration of the medical periodic table: towards new targets.

PubMed

Barry, Nicolas P E; Sadler, Peter J

2013-06-07

Metallodrugs offer potential for unique mechanisms of drug action based on the choice of the metal, its oxidation state, the types and number of coordinated ligands and the coordination geometry. We discuss recent progress in identifying new target sites and elucidating the mechanisms of action of anti-cancer, anti-bacterial, anti-viral, anti-parasitic, anti-inflammatory, and anti-neurodegenerative agents, as well as in the design of metal-based diagnostic agents. Progress in identifying and defining target sites has been accelerated recently by advances in proteomics, genomics and metal speciation analysis. Examples of metal compounds and chelating agents (enzyme inhibitors) currently in clinical use, clinical trials or preclinical development are highlighted.

Uptake, localization, and speciation of cobalt in Triticum aestivum L. (wheat) and Lycopersicon esculentum M. (tomato).

PubMed

Collins, Richard N; Bakkaus, Estelle; Carrière, Marie; Khodja, Hicham; Proux, Olivier; Morel, Jean-Louis; Gouget, Barbara

2010-04-15

The root-to-shoot transfer, localization, and chemical speciation of Co were investigated in a monocotyledon (Triticum aestivum L., wheat) and a dicotyledon (Lycopersicon esculentum M., tomato) plant species grown in nutrient solution at low (5 muM) and high (20 muM) Co(II) concentrations. Cobalt was measured in the roots and shoots by inductively coupled plasma-mass spectrometry. X-ray absorption spectroscopy measurements were used to identify the chemical structure of Co within the plants and Co distribution in the leaves was determined by micro-PIXE (particle induced X-ray emission). Although the root-to-shoot transport was higher for tomato plants exposed to excess Co, both plants appeared as excluders. The oxidation state of Co(II) was not transformed by either plant in the roots or shoots and Co appeared to be present as Co(II) in a complex with carboxylate containing organic acids. Cobalt was also essentially located in the vascular system of both plant species indicating that neither responded to Co toxicity via sequestration in epidermal or trichome tissues as has been observed for other metals in metal hyperaccumulating plants.

X-ray absorption near-edge structure micro-spectroscopy study of vanadium speciation in Phycomyces blakesleeanus mycelium.

PubMed

Žižić, Milan; Dučić, Tanja; Grolimund, Daniel; Bajuk-Bogdanović, Danica; Nikolic, Miroslav; Stanić, Marina; Križak, Strahinja; Zakrzewska, Joanna

2015-09-01

Vanadium speciation in the fungus Phycomyces blakesleeanus was examined by X-ray absorption near-edge structure (XANES) spectroscopy, enabling assessment of oxidation states and related molecular symmetries of this transition element in the fungus. The exposure of P. blakesleeanus to two physiologically important vanadium species (V(5+) and V(4+)) resulted in the accumulation of this metal in central compartments of 24 h old mycelia, most probably in vacuoles. Tetrahedral V(5+), octahedral V(4+), and proposed intracellular complexes of V(5+) were detected simultaneously after addition of a physiologically relevant concentration of V(5+) to the mycelium. A substantial fraction of the externally added V(4+) remained mostly in its original form. However, observable variations in the pre-edge-peak intensities in the XANES spectra indicated intracellular complexation and corresponding changes in the molecular coordination symmetry. Vanadate complexation was confirmed by (51)V NMR and Raman spectroscopy, and potential binding compounds including cell-wall constituents (chitosan and/or chitin), (poly)phosphates, DNA, and proteins are proposed. The evidenced vanadate complexation and reduction could also explain the resistance of P. blakesleeanus to high extracellular concentrations of vanadium.

Iron Speciation and Mixing in Single Aerosol Particles from the Asian Continental Outflow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moffet, Ryan C.; Furutani, Hiroshi; Rodel, Tobias

2012-04-04

Bioavailable iron from atmospheric aerosol is an essential nutrient that can control oceanic productivity, thereby impacting the global carbon budget and climate. Particles collected on Okinawa Island during an atmospheric pollution transport event from China were analyzed using complementary single particle techniques to determine the iron source and speciation. Comparing the spatial distribution of iron within ambient particles and standard Asian mineral dust, it was determined that field-collected atmospheric Fe-containing particles have numerous sources, including anthropogenic sources such as coal combustion. Fe-containing particles were found to be internally mixed with secondary species such as sulfate, soot, and organic carbon. Themore » mass weighted average Fe(II) fraction (defined as Fe(II)/[Fe(II)+Fe(III)]) was determined to be 0.33 {+-} 0.08. Within the experimental uncertainty, this value lies close to the range of 0.26-0.30 determined for representative Asian mineral dust. Previous studies have indicated that the solubility of iron from combustion is much higher than that from mineral dust. Therefore, chemical and/or physical differences other than oxidation state may help explain the higher solubility of iron in atmospheric particles.« less

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

PubMed Central

Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.

2016-01-01

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465

Speciation studies of nickel and chromium in wastewater from an electroplating plant.

PubMed

Kiptoo, Jackson K; Ngila, J Catherine; Sawula, Gerald M

2004-09-08

A speciation scheme involving the use of flame atomic absorption spectrometry (FAAS) and differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV) techniques was applied to studies of nickel and chromium in wastewater from a nickel-chrome electroplating plant. Dimethylglyoxime (DMG) and diethylenetriaminepentaacetic acid (DTPA) were employed as complexing agents for adsorptive voltammetric determination of Ni and Cr, respectively. Cr(III) and Cr(VI) were determined by exploiting differences in their reactivity towards DTPA at HMDE. Total dissolved metal content was in the range 2906-3141 and 30.7-31.2mgl(-1) for Ni and Cr, respectively. A higher percentage of the metal was present as labile species (mean value of 67.9% for Ni and 79.8% for Cr) suggesting that strongly binding ligands are not ubiquitous in the sample. About 77.8% of Cr was found to exist in the higher oxidization state, Cr(IV). Results on effect of dilution on lability of the metal forms in the sample using DPAdCSV showed slight peak shifts to a more negative (cathodic) value by -0.036V for Ni and -0.180V for Cr with a dilution factor of 100, while peak intensity (cathodic current) remained fairly constant.

The analysis of forms of sulfur in ancient sediments and sedimentary rocks: comments and cautions

USGS Publications Warehouse

Rice, C.A.; Tuttle, M.L.; Reynolds, R.L.

1993-01-01

Assumptions commonly made during analysis of the amount of monosulfides [acid-volatile sulfides (AVS)] and disulfides in modern sediments, may not be valid for ancient sedimentary rocks. It is known that ferric iron can oxidize H2S during AVS analysis unless a reducing agent such as stannous chloride is added to the treatment. In addition, some monosulfides such as greigite and pyrrhotite require heat during the AVS analysis in order to dissolve completely. However, the use of heat and/or stannous chloride in the AVS treatment may partially dissolve disulfides and it is generally recommended that stannous chloride not be used in the AVS treatment for modern sediments. Most of the monosulfides are assumed to be recovered as AVS without the addition of stannous chloride. This study investigates the recovery of monosulfides during sulfur speciation analysis with application to ancient sedimentary rocks. Sulfur in samples containing naturally occurring greigite and mackinawite or pyrite was measured using variations of a common sulfur-speciation scheme. The sulfur-speciation scheme analyzes for monosulfide sulfur, disulfide sulfur, elemental sulfur, inorganic sulfate and organically bound sulfur. The effects of heat, stannous chloride and ferric iron on the amounts of acid-volatile sulfide and disulfide recovered during treatment for AVS were investigated. Isotopic compositions of the recovered sulfur species along with yields from an extended sulfur-speciation scheme were used to quantify the effects. Hot 6 N HCl AVS treatment recovers > 60% of the monosulfides as AVS in samples containing pure greigite and mackinawite. The remaining monosulfide sulfur is recovered in a subsequent elemental sulfur extraction. Hot 6 N HCl plus stannous chloride recovers 100% of the monosulfides as AVS. The addition of ferric iron to pure greigite and mackinawite samples during AVS treatment without stannous chloride decreased the amount of monosulfides recovered as AVS and, if present in great enough concentration, oxidized some of the AVS to a form not recovered in later treatments. The hot stannous chloride AVS treatments dissolve <5% of well-crystallized pyrite in this study. The amount of pyrite dissolved depends on grain size and crystallinity. Greigite in ancient sedimentary rocks was quantitatively recovered as AVS only with hot 6 N HCl plus stannous chloride. Hot 6 N HCl AVS treatment of these rocks did not detect any monosulfides in most samples. A subsequent elemental sulfur extraction did not completely recover the oxidized monosulfides. Therefore, the use of stannous chloride plus heat is recommended in the AVS treatment of ancient sedimentary rocks if monosulfides are present and of interest. All assumptions about the amount of monosulfides and disulfides recovered with the sulfur-speciation scheme used should be verified by extended sulfur-speciation and/or isotopic analysis of the species recovered. ?? 1993.

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

USGS Publications Warehouse

Gandhi, N.; Bhavsar, S.P.; Diamond, M.L.; Kuwabara, J.S.; Marvin-DiPasquale, M.; Krabbenhoft, D.P.

2007-01-01

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)2, and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations. ?? 2007 SETAC.

Fate of copper complexes in hydrothermally altered deep-sea sediments from the Central Indian Ocean Basin.

PubMed

Chakraborty, Parthasarathi; Sander, Sylvia G; Jayachandran, Saranya; Nath, B Nagender; Nagaraju, G; Chennuri, Kartheek; Vudamala, Krushna; Lathika, N; Mascarenhas-Pereira, Maria Brenda L

2014-11-01

The current study aims to understand the speciation and fate of Cu complexes in hydrothermally altered sediments from the Central Indian Ocean Basin and assess the probable impacts of deep-sea mining on speciation of Cu complexes and assess the Cu flux from this sediment to the water column in this area. This study suggests that most of the Cu was strongly associated with different binding sites in Fe-oxide phases of the hydrothermally altered sediments with stabilities higher than that of Cu-EDTA complexes. The speciation of Cu indicates that hydrothermally influenced deep-sea sediments from Central Indian Ocean Basin may not significantly contribute to the global Cu flux. However, increasing lability of Cu-sediment complexes with increasing depth of sediment may increase bioavailability and Cu flux to the global ocean during deep-sea mining. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mechanisms of Arsenic Mobilization and Attenuation in Subsurface Sediments

NASA Astrophysics Data System (ADS)

O'Day, P. A.; Illera, V.; Root, R.; Choi, S.; Vlassopoulos, D.

2007-12-01

This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited in labile or available S and/or Fe that remove As by precipitation or adsorption. In subsurface sediments with low labile S and Fe, laboratory experiments and spectroscopic studies suggest that sediment Mn minerals are important in the oxidation of sorbed As(III) to As(V), but that they have a limited oxidation capacity. Arsenic attenuation and mobilization in the subsurface are affected by seasonal variations when hydraulic conditions are influenced by surface infiltration, which may induce transitions from oxidized to reduced conditions (or vice versa) in porewater.

Effect of uranium(VI) speciation on simultaneous microbial reduction of uranium(VI) and iron(III).

PubMed

Stewart, Brandy D; Amos, Richard T; Fendorf, Scott

2011-01-01

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.

Bioavailability of cadmium adsorbed on various oxides minerals to wetland plant species Phragmites australis.

PubMed

Wang, He; Jia, Yongfeng; Wang, Shaofeng; Zhu, Huijie; Wu, Xing

2009-08-15

The bioavailability of heavy metals strongly depends on their speciation in the environment. The effect of different chemical speciations of cadmium ions (i.e. adsorbed on different oxide minerals) on its bioavailability to wetland plant Phragmites australis was studied. Goethite, magnetite, gibbsite, alumina, and manganese oxide were chosen as representatives of metal (hydr)oxides commonly present in sediment. The cultivar system with Hoagland solution as nutrition supply, and single metal oxide with adsorbed Cd as contaminant was applied to study Cd accumulation by P. australis. The bioaccumulation degree in root after the 45-day treatment followed the order: Al(OH)(3)>Al(2)O(3)>Fe(3)O(4)>MnO(2)>FeOOH. The concentration of Cd in stem and leaf followed a similar order although it was considerably lower than that in root. Low-molecular-weight organic acids (LMWOAs), acetic acid, malic acid and citric acid were used to evaluate the desorbability of Cd from different oxides, which can be indicative of Cd-oxide bonding strength and Cd bioavailability. Desorption of Cd by acetic acid and malic acid followed the order: Al(OH)(3)>Fe(3)O(4)>Al(2)O(3)>FeOOH>MnO(2), while by citric acid: Al(OH)(3)> or =Al(2)O(3)>Fe(3)O(4)>FeOOH>MnO(2). This was consistent with the Cd accumulation degree in the plant. Cd adsorbed on Al(OH)(3) was the most easily desorbable species and most bioavailable to P. australis among the oxide minerals, whereas MnO(2) adsorbed Cd was least desorbable by LMWOAs hence constituted the least bioavailable Cd species adsorbed on the oxide minerals.

Modification of an Existing In vitro Method to Predict Relative ...

EPA Pesticide Factsheets

The soil matrix can sequester arsenic (As) and reduces its exposure by soil ingestion. In vivo dosing studies and in vitro gastrointestinal (IVG) methods have been used to predict relative bioavailable (RBA) As. Originally, the Ohio State University (OSU-IVG) method predicted RBA As for soils exclusively from mining and smelting sites with a median of 5,636 mg As kg-1. The objectives of the current study were to (i) evaluate the ability of the OSU-IVG method to predict RBA As for As contaminated soils with a wider range of As content and As contaminant sources, and (ii) evaluate a modified extraction procedure's ability to improve prediction of RBA As. In vitro bioaccessible (IVBA) by OSU-IVG and California Bioaccessibility Method (CAB) methods, RBA As, speciation, and properties of 33 As contaminated soils were determined. Total As ranged from 162 to 12,483 mg kg-1 with a median of 731 mg kg-1. RBA As ranged from 1.30 to 60.0% and OSU-IVG IVBA As ranged from 0.80 to 52.3%. Arsenic speciation was predominantly As(V) adsorbed to hydrous ferric oxide (HFO) or iron (Fe), manganese (Mn), and aluminum (Al) oxides. The OSU-IVG often extracted significantly less As in vitro than in vivo RBA As, in particularly for soils from historical gold mining. The CAB method, which is a modified OSU-IVG method extracted more As than OSU-IVG for most soils, resulting in a more accurate predictor than OSU-IVG, especially for low to moderately contaminated soils (<1,500 mg As

Speciation of Phosphorus by coupled HPLC-ICPMS: Application for quantification of reduced forms of phosphorus in rocks and natural waters.

NASA Astrophysics Data System (ADS)

Atlas, Z. D.; Pasek, M. A.; Sampson, J.

2014-12-01

Phosphorus is a geologically important element making up approximately 0.12 % of the Earth's crust. It is commonly found as relatively insoluble apatite and this causes phosphorus to be a limiting nutrient in biologic processes. Despite this, phosphorus is a key element in DNA, RNA and other cellular materials. Recent works suggest that reduced phosphorus played a substantial role in the development of life on the early Earth. Reduced phosphorus is considerably more soluble than oxidized phosphorus, and reduced phosphorus may continue to play a role in biologic productivity. This study examines a new methodology for quantification of reduced phosphorus separated by coupled HPLC - ICP-MS. We show that phosphorus species (P1+, P3+ and P5+) are cleanly separated in the HPLC and coupled with the ICP-MS reaction cell (using O2 gas) effectively convert elemental P to P-O producing lower background and flatter baseline chromatography. Results suggest very low detection limits (0.05 mM) for P species analyzed as P-O at M/Z = 47. Additionally this technique has potential to speciate at least 5 other metastable forms of phosphorus. We verified this method on numerous materials including leached Archean rocks to suburban retention pond waters and many samples show small but detectible levels of reduced phosphorus. These data highlight a significant role of redox processing of phosphorus throughout the history of the Earth, with the reduced oxidation state phosphorus compounds, phosphite and hypophosphite, potentially acting as significant constituents in the anaerobic environment.

Systemic distribution and speciation of diphenylarsinic acid fed to rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naranmandura, Hua; Analytical and Environmental Toxicology, Department of Laboratory Medicine and Pathology, University of Alberta, Edmonton, Alberta, T6G 2G3; Suzuki, Noriyuki

Diphenylarsinic acid (DPAA) is an environmental degradation product of diphenylarsine chloride or diphenylarsine cyanide, which were chemical warfare agents produced by Japan during the World War II. DPAA is now considered a dangerous environmental pollutant in Kamisu, Japan, where it is suspected of inducing health effects that include articulation disorders (cerebellar ataxia of the extremities and trunk), involuntary movements (myoclonus and tremor), and sleep disorders. In order to elucidate the toxic mechanism of DPAA, we focused on the distribution and metabolism of DPAA in rats. Systemic distribution of DPAA was determined by administering DPAA orally to rats at a singlemore » dose of 5.0 mg As/kg body weight, followed by speciation analysis of selected organs and body fluids. Most of the total arsenic burden was recovered in the urine (23% of the dose) and feces (27%), with the distribution in most other organs/tissues being less than 1%. However, compared with the typical distribution of inorganic dietary arsenic, DPAA administration resulted in elevated levels in the brain, testes and pancreas. In contrast to urine, in which DPAA was found mostly in its unmodified form, the tissues and organs contained arsenic that was mostly bound to non-soluble and soluble high molecular weight proteins. These bound arsenic species could be converted back to DPAA after oxidation with H{sub 2}O{sub 2}, suggesting that the DPAA bound to proteins had been reduced within the body and was in a trivalent oxidation state. Furthermore, we also detected two unknown arsenic metabolites in rat urine, which were assumed to be hydroxylated arsenic metabolites.« less

EFFECTS OF FLY ASH TRANSITION METAL CONTENT AND FLUE GAS HCL/SO2 RATIO ON MERCURY SPECIATION IN WASTE COMBUSTION

EPA Science Inventory

The paper presents results of research on the effect of sulfur dioxide (SO2):HCI ratio on heterogeneous Hg0 oxidation. The addition of SO2 to moist flue gas at high SO2:HCI ratios (4:1 to 10:1) caused a decrease in oxidation of Hg0 relative to flur gas without SO2. This is attrib...

Formation of soluble mercury oxide coatings: Transformation of elemental mercury in soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Carrie L.; Watson, David B.; Lester, Brian P.

2015-09-21

In this study, the impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reactingmore » with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.« less

How does organic matter occurrence set limit onto the use of Ce anomaly as a reliable proxy of redox conditions in shallow groundwaters?

NASA Astrophysics Data System (ADS)

Dia, A.; Gruau, G.; Davranche, M.; Vidy, A.; Henin, O.; Petitjean, P.; Le Coz-Bouhnik, M.

2003-04-01

This study is dedicated to the effects of organic matter on the hydrochemistry of Rare Earth Elements (REE) and the ability of using the Ce anomaly as a reliable proxy of redox conditions in surface waters when organic matter occurs. The data include a : i) two-year survey of SREE and Ce anomalies in organic-rich waters recovered from a catchment located in Brittany (western Europe) and (ii) experimental incubation of organic soils from this catchment set under controlled conditions, as well as, (iii) a REE speciation calculation in both the natural organic-rich waters from the wetlands and the experimental solutions. Field and experimental data appear to be extremely coherent, displaying good correlation between the SREE, the Dissolved Organic Carbon (DOC) contents and the redox state. The field data show a strong increase of the SREE and DOC concentrations in soil waters when the environment becomes more reducing. The onset of DOC and SREE contents is seen to be in phase with the increase of dissolved Fe and Mn. The role of Fe-, Mn-oxyhydroxides is confirmed by the experimental data as the maximum of DOC and SREE content is reached when Fe2+ reaches a maximum in the soil solution, suggesting that reductive dissolution of Fe, Mn-oxyhydroxides happens. Despite the strong redox changes and the known redox sensitive behaviour of Ce as compared to other REE, none Ce anomaly variation is observed during either, the experimental procedure, or the field survey through time. Speciation calculations were performed showing that in both such pH range and moderately oxidizing waters in DOC-rich waters, REE should have an organic speciation. Such an organic speciation prevents the formation of Ce(IV) and therefore the development of any Ce anomaly. However, since the studied waters are highly oxidizing (high nitrate contents), the nitrates impose the redox formation of Ce(IV) and a Ce anomaly should appear. Therefore, Ce(IV) is not formed in these waters either because (i) the reaction kinetic might be so slow that the anomaly has no time to ever happen in the field, or (ii) Ce(IV) might be linked to the organic colloidal fraction. Since the thermodynamic modelling does not help getting information, further experimental kinetics or ultrafiltration studies will be required to clarify these latter points. This has to be fixed to be able to use the Ce anomaly as a reliable proxy of redox conditions in organic-rich environment.

Chemistry of transuranium elements in salt-base repository

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borkowski, Marian; Reed, Donald T; Lucchini, Jean - Francois

2010-12-02

The mobility and potential release of actinides into the accessible environment continues to be the key performance assessment concern of nuclear repositories. Actinide, in particular plutonium speciation under the wide range of conditions that can exist in the subsurface is complex and depends strongly on the coupled effects of redox conditions, inorganic/organic complexation, and the extent/nature of aggregation. Understanding the key factors that define the potential for actinide migration is, in this context, an essential and critical part of making and sustaining a licensing case for a nuclear repository. Herein we report on recent progress in a concurrent modeling andmore » experimental study to determine the speciation of plutonium, uranium and americium in high ionic strength Na-CI-Mg brines. This is being done as part of the ongomg recertification effort m the Waste Isolation Pilot Plant (WIPP). The oxidation-state specific solubility of actinides were established in brine as function of pC{sub H+}, brine composition and the presence and absence of organic chelating agents and carbonate. An oxidation-state invariant analog approach using Nd{sup 3+} and Th{sup 4+} was used for An{sup 3+} and An{sup 4+} respectively. These results show that organic ligands and hydrolysis are key factors for An(III) solubility, hydrolysis at pC{sub H+} above 8 is predominate for An(IV) and carbonates are the key factor for U(VI) solubility. The effect of high ionic strength and brine components measured in absence of carbonates leads to measurable increased in overall solubility over analogous low ionic strength groundwater. Less is known about the bioreduction of actinides by halo-tolerant microorganisms, but there is now evidence that bioreduction does occur and is analogous, in many ways, to what occurs with soil bacteria. Results of solubility studies that focus on Pitzer parameter corrections, new species (e.g. borate complexation), and the thermodynamic parameters for modeling are discussed.« less

Sulfur redox chemistry governs diurnal antimony and arsenic cycles at Champagne Pool, Waiotapu, New Zealand

NASA Astrophysics Data System (ADS)

Ullrich, Maria K.; Pope, James G.; Seward, Terry M.; Wilson, Nathaniel; Planer-Friedrich, Britta

2013-07-01

Champagne Pool, a sulfidic hot spring in New Zealand, exhibits distinct diurnal variations in antimony (Sb) and arsenic (As) concentrations, with daytime high and night-time low concentrations. To identify the underlying mobilization mechanisms, five sites along the drainage channel of Champagne Pool were sampled every 2 h during a 24 h period. Temporal variations in elemental concentrations and Sb, As, and sulfur (S) speciation were monitored in the discharging fluid. Total trace element concentrations in filtered and unfiltered samples were analyzed using ICP-MS, and Sb, As and S species were determined by IC-ICP-MS. Sulfur speciation in the drainage channel was dominated by thiosulfate and sulfide at night, while sulfate dominated during the day. The distinct diurnal changes suggest that the transformations are caused by phototrophic sulfur-oxidizing bacteria. These bacteria metabolize thiosulfate and sulfide in daylight to form sulfate and, as suggested by modeling with PhreeqC, elemental sulfur. Sulfide consumption during the day results in undersaturation of antimony sulfides, which triggers the additional release of dissolved Sb. For As, diurnal cycles were much more pronounced in speciation than in total concentrations, with di- and trithioarsenate forming at night due to excess sulfide, and monothioarsenate forming from arsenite and elemental sulfur during the day. Sulfur speciation was thus found to control Sb and As in terms of both solubility and speciation.

Stability of oxidized iron species and the redox budget of slab-derived fluids

NASA Astrophysics Data System (ADS)

Sanchez-Valle, C.; Hin, R.; Testemale, D.; Borca, C.; Grolimund, D.

2017-12-01

The high oxidation state of subduction zone magmas compared to magmas from other locations might result from the influx of oxidized fluid from the subducted oceanic plate into the mantle wedge. However, the nature of the chemical agent(s) and the mechanism responsible for the transfer of the oxidized signature from the slab to the mantle wedge remains poorly understood. In this contribution, we will discuss the oxidizing capacity of slab-derived fluids in the light of experimental results of the solubility and speciation of iron in high-pressure fluids that mimic the slab flux. Iron-bearing mineral assemblages were equilibrated with chlorinated aqueous fluids and hydrous granitic melts at different oxygen fugacities relevant for the present day crust/mantle. The concentration of iron and the distribution of stability of oxidized iron species were monitored up to 2.5 GPa and 800 °C using a combination of diamond trap experiments and XANES measurements in diamond anvil cells. The results illustrate the role of coordination chemistry involving halogen and polymerized species in the stability of oxidized iron in the fluids. The concentration of Fe3+ in the fluids progressively decreases as temperature increases, regardless of fluid composition and pressure. This implies that the fluid capacity to transport Fe3+ at high temperature may be limited, even at the redox conditions relevant for the present day crust and mantle. With the new experimental results, we place constrains on the oxidizing capacity of Fe-bearing metasomatic fluids and discuss the transfer of the oxidizing signature and the conditions for the genesis of oxidized arc magmas.

Particles, sweat, and tears: a comparative study on bioaccessibility of ferrochromium alloy and stainless steel particles, the pure metals and their metal oxides, in simulated skin and eye contact.

PubMed

Hedberg, Yolanda; Midander, Klara; Wallinder, Inger Odnevall

2010-07-01

Ferrochromium alloys are manufactured in large quantities and placed on the global market for use as master alloys (secondary raw materials), primarily for stainless steel production. Any potential human exposure to ferrochromium alloy particles is related to occupational activities during production and use, with 2 main exposure routes, dermal contact and inhalation and subsequent digestion. Alloy and reference particles exposed in vitro in synthetic biological fluids relevant for these main exposure routes have been investigated in a large research effort combining bioaccessibility; chemical speciation; and material, surface, and particle characteristics. In this paper, data for the dermal exposure route, including skin and eye contact, will be presented and discussed. Bioaccessibility data have been generated for particles of a ferrochromium alloy, stainless steel grade AISI 316L, pure Fe, pure Cr, iron(II,III)oxide, and chromium(III)oxide, upon immersion in artificial sweat (pH 6.5) and artificial tear (pH 8.0) fluids for various time periods. Measured released amounts of Fe, Cr, and Ni are presented in terms of average Fe and Cr release rates and amounts released per amount of particles loaded. The results are discussed in relation to bulk and surface composition of the particles. Additional information, essential to assess the bioavailability of Cr released, was generated by determining its chemical speciation and by providing information on its complexation and oxidation states in both media investigated. The effect of differences in experimental temperature, 30 degrees C and 37 degrees C, on the extent of metal release in artificial sweat is demonstrated. Iron was the preferentially released element in all test media and for all time periods and iron-containing particles investigated. The extent of metal release was highly pH dependent and was also dependent on the medium composition. Released amounts of Cr and Fe were very low (close to the limit of detection, <0.008% of particles released or dissolved as iron or chromium) for the alloy particles (ferrochromium alloy and stainless steel), the pure Cr particles, and the metal oxide particles. The released fraction of Cr (Cr/[Cr + Fe]) varied with the material investigated, the test medium, and the exposure time and cannot be predicted from either the bulk or the surface composition. Chromium was released as noncomplexed Cr(III) and in addition in very low concentrations (<3 microg/L). Nickel released was under the limit of detection (0.5 microg/L), except for ultrafine stainless steel particles (<10 microg/L). It is evident that media chemistry and material properties from a bulk and surface perspective, as well as other particle characteristics, and the chemical speciation of released metals have to be considered when assessing any potential hazard or risk induced by sparingly soluble metal or alloy particles. (c) 2010 SETAC.

Arsenic Species in Drinking Water Wells in the USA with High Arsenic Concentrations

EPA Science Inventory

As part of the United States Environmental Protection Agency (USEPA) arsenic treatment demonstration program, 65 five well waters scattered across the US were speciated for As(III) and As(V). The speciation test data showed that most (60) well waters had one dominant species, but...

Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

NASA Astrophysics Data System (ADS)

Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

2003-04-01

Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key groundwater constituents in our data suggest that arsenic is released due to the reductive dissolution of arsenic laden-hydrous ferric oxides, however, further work is required to fully evaluate the mode of arsenic release.

SAMPLING ARTIFACT ESTIMATES FOR ALKANES, HOPANES, AND ALIPHATIC CARBOXYLIC ACIDS

EPA Science Inventory

Sampling artifacts for molecular markers from organic speciation of particulate matter were investigated by analyzing forty-one samples collected in Philadelphia as a part of the Northeast Oxidant and Particulate Study (NEOPS). Samples were collected using a high volume sampler ...

BROMIDE'S EFFECT ON DBP FORMATION, SPECIATION, AND CONTROL: PART 1, OZONATION

EPA Science Inventory

The effect of variable ozone dosage and bromide concentration on the formation of organic disinfection byproducts (DBPs) and bromate were evaluated. Low ozone dosages resulted in oxidation of organic precursors, yielding decreases in the formation potential for total trihalometha...

A robust framework to predict mercury speciation in combustion flue gases.

PubMed

Ticknor, Jonathan L; Hsu-Kim, Heileen; Deshusses, Marc A

2014-01-15

Mercury emissions from coal combustion have become a global concern as growing energy demands have increased the consumption of coal. The effective implementation of treatment technologies requires knowledge of mercury speciation in the flue gas, namely concentrations of elemental, oxidized and particulate mercury at the exit of the boiler. A model that can accurately predict mercury species in flue gas would be very useful in that context. Here, a Bayesian regularized artificial neural network (BRANN) that uses five coal properties and combustion temperature was developed to predict mercury speciation in flue gases before treatment technology implementation. The results of the model show that up to 97 percent of the variation in mercury species concentration is captured through the use of BRANNs. The BRANN model was used to conduct a parametric sensitivity which revealed that the coal chlorine content and coal calorific value were the most sensitive parameters, followed by the combustion temperature. The coal sulfur content was the least important parameter. The results demonstrate the applicability of BRANNs for predicting mercury concentration and speciation in combustion flue gas and provide a more efficient and effective technique when compared to other advanced non-mechanistic modeling strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

Study of sulfur bonding on gallium arsenide (100) surfaces using supercritical fluid extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cabauy, P.; Darici, Y.; Furton, K.G.

1995-12-01

In the last decades Gallium Arsenide (GaAs) has been considered the semiconductor that will replace silicon because of its direct band gap and high electron mobility. Problems with GaAs Fermi level pinning has halted its widespread use in the electronics industry. The formation of oxides on GaAs results in a high density of surface states that effectively pin the surface Fermi level at the midgap. Studies on sulfur passivation have eliminated oxidation and virtually unpinned the Fermi level on the GaAs surface. This has given rise to interest in sulfur-GaAs bonds. In this presentation, we will discuss the types ofmore » sulfur bonds extracted from a sulfur passivated GaAs (100) using Supercritical Fluid (CO2) Extraction (SFE). SFE can be a valuable tool in the study of chemical speciations on semiconductor surfaces. The variables evaluated to effectively study the sulfur species from the GaAs surface include passivation techniques, supercritical fluid temperatures, densities, and extraction times.« less

Microbial Transformation of Iodine: From Radioisotopes to Iodine Deficiency.

PubMed

Yeager, Chris M; Amachi, Seigo; Grandbois, Russell; Kaplan, Daniel I; Xu, Chen; Schwehr, Kathy A; Santschi, Peter H

2017-01-01

Iodine is a biophilic element that is important for human health, both as an essential component of several thyroid hormones and, on the other hand, as a potential carcinogen in the form of radioiodine generated by anthropogenic nuclear activity. Iodine exists in multiple oxidation states (-1, 0, +1, +3, +5, and +7), primarily as molecular iodine (I 2 ), iodide (I - ), iodate [Formula: see text] , or organic iodine (org-I). The mobility of iodine in the environment is dependent on its speciation and a series of redox, complexation, sorption, precipitation, and microbial reactions. Over the last 15years, there have been significant advances in iodine biogeochemistry, largely spurred by renewed interest in the fate of radioiodine in the environment. We review the biogeochemistry of iodine, with particular emphasis on the microbial processes responsible for volatilization, accumulation, oxidation, and reduction of iodine, as well as the exciting technological potential of these fascinating microorganisms and enzymes. Copyright © 2017 Elsevier Inc. All rights reserved.

Microbial mobilization of plutonium and other actinides from contaminated soil

DOE PAGES

Francis, A. J.; Dodge, C. J.

2015-12-01

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Microbial mobilization of plutonium and other actinides from contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Francis, A. J.; Dodge, C. J.

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Aluminum and Fenton reaction: how can the reaction be modulated by speciation? A computational study using citrate as a test case.

PubMed

Mujika, Jon I; Dalla Torre, Gabriele; Lopez, Xabier

2018-06-13

The pro-oxidant ability of aluminum is behind many of the potential toxic effects of this exogenous element in the human organism. Although the overall process is still far from being understood at the molecular level, the well known ability of aluminum to promote the Fenton reaction is mediated through the formation of stable aluminum-superoxide radical complexes. However, the properties of metal complexes are highly influenced by the speciation of the metal. In this paper, we investigate the effect that speciation could have on the pro-oxidant activity of aluminum. We choose citrate as a test case, because it is the main low-molecular-mass chelator of aluminum in blood serum, forming very stable aluminum-citrate complexes. The influence of citrate in the interaction of aluminum with the superoxide radical is investigated, determining how the formation of aluminum-citrate complexes affects the promotion of the Fenton reaction. The results indicate that citrate increases the stability of the aluminum-superoxide complexes through the formation of ternary compounds, and that the Fenton reaction is even more favorable when aluminum is chelated to citrate. Nevertheless, our results demonstrate that overall, citrate may prevent the pro-oxidant activity of aluminum: on one hand, in an excess of citrate, the formation of 1 : 2 aluminum-citrate complexes is expected. On the other hand, the chelation of iron by citrate makes the reduction of iron thermodynamically unfavorable. In summary, the results suggest that citrate can have both a promotion and protective role, depending on subtle factors, such as initial concentration, non-equilibrium behavior and the exchange rate of ligands in the first shell of the metals.

Simulation of SOA formation and composition from oxidation of toluene and m-xylene in chamber experiments

NASA Astrophysics Data System (ADS)

Xu, J.; Liu, Y.; Nakao, S.; Cocker, D.; Griffin, R. J.

2013-12-01

Aromatic hydrocarbons contribute an important fraction of anthropogenic reactive volatile organic compounds (VOCs) in the urban atmosphere. Photo-oxidation of aromatic hydrocarbons leads to secondary organic products that have decreased volatilities or increased solubilities and can form secondary organic aerosol (SOA). Despite the crucial role of aromatic-derived SOA in deteriorating air quality and harming human health, its formation mechanism is not well understood and model simulation of SOA formation still remains difficult. The dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. Most models predict SOA formation under high NOx levels well but underestimate SOA formation under low NOx levels more representative of the ambient atmosphere. Thus, it is crucial to investigate the NOx-dependent chemistry in aromatic photo-oxidation systems and correspondingly update SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparing to eighteen University of California, Riverside United States Environmental Protection Agency (EPA) chamber experiment runs under both high and low NOx conditions. Correction factors for vapor pressures imply uncharacterized aerosol-phase association chemistry. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to 40%~60% for both aromatics). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Speciation distributions under varied NOx levels implies that the well-known competition between RO2 + HO2 and RO2 + NO (RO2 = peroxide bicyclic radical) may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with its self-cyclization also affects NOx-dependence of SOA formation. Comparison of SOA formation yield and composition between two aromatics implies aldehyde/ketone chemistry from ring-opening route and chemistry for phenolic route play important roles in governing SOA formation and that ring-opening aldehydes and phenolic nitrates are produced to a greater extent in the toluene system, leading to higher SOA yields for toluene than for m-xylene.

Environmental microbes can speciate and cycle arsenic.

PubMed

Rhine, E Danielle; Garcia-Dominguez, Elizabeth; Phelps, Craig D; Young, L Y

2005-12-15

Naturally occurring arsenic is found predominantly as arsenate [As(V)] or arsenite [As(III)], and can be readily oxidized or reduced by microorganisms. Given the health risks associated with arsenic in groundwater and the interest in arsenic-active microorganisms, we hypothesized that environmental microorganisms could mediate a redox cycling of arsenic that is linked to their metabolism. This hypothesis was tested using an As(V) respiring reducer (strain Y5) and an aerobic chemoautotrophic As(II) oxidizer (strain OL1 ) both isolated from a Superfund site, Onondaga Lake, in Syracuse, NY. Strains were grown separately and together in sealed serum bottles, and the oxic/anoxic condition was the only parameter changed. Initially, under anoxic conditions when both isolates were grown together, 2 mM As(V) was stoichiometrically reduced to As(III) within 14 days. Following complete reduction, sterile ambient air was added and within 24 h As(III) was completely oxidized to As(V). The anoxic-oxic cycle was repeated, and sterile controls showed no abiotic transformation within the 28-day incubation period. These results demonstrate that microorganisms can cycle arsenic in response to dynamic environmental conditions, thereby affecting the speciation, and hence mobility and toxicity of arsenic in the environment.

Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

PubMed

Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

2013-02-21

A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

Investigation of processes controlling summertime gaseous elemental mercury oxidation at midlatitudinal marine, coastal, and inland sites

NASA Astrophysics Data System (ADS)

Ye, Zhuyun; Mao, Huiting; Lin, Che-Jen; Kim, Su Youn

2016-07-01

A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate the oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (AI; marine), Thompson Farm (TF; coastal, rural), and Pack Monadnock (PM; inland, rural, elevated). The chemical mechanism in this box model included the most up-to-date Hg and halogen chemistry. As a result, the box model was able to simulate reasonably the observed diurnal cycles of gaseous oxidized mercury (GOM) and chemical speciation bearing distinct differences between the three sites. In agreement with observations, simulated GOM diurnal cycles at AI and TF showed significant daytime peaks in the afternoon and nighttime minimums compared to flat GOM diurnal cycles at PM. Moreover, significant differences in the magnitude of GOM diurnal amplitude (AI > TF > PM) were captured in modeled results. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80-99 % of total GOM production during daytime. H2O2-initiated GEM oxidation was significant (˜ 33 % of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL) atmosphere, Br and BrO became dominant GEM oxidants, with mixing ratios reaching 0.1 and 1 pptv, respectively, and contributing ˜ 70 % of the total GOM production during midday, while O3 dominated GEM oxidation (50-90 % of GOM production) over the remaining day when Br and BrO mixing ratios were diminished. The majority of HgBr produced from GEM+Br was oxidized by NO2 and HO2 to form brominated GOM species. Relative humidity and products of the CH3O2+BrO reaction possibly significantly affected the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas-particle partitioning could potentially be important in the production of GOM as well as Br and BrO at the marine site.

Sulfur Speciation in Peat: a Time-zero Signature for the " Spruce and Peatland Responses Under Climate and Environmental Change" Experiment

NASA Astrophysics Data System (ADS)

Furman, O.; Toner, B. M.; Sebestyen, S. D.; Kolka, R. K.; Nater, E. A.

2014-12-01

As part of the "Spruce and Peatland Responses Under Climate and Environmental Change" (SPRUCE) experiment, we made initial measurements of sulfur speciation in peat. These observations represent a "time-zero" relative to the intended soil warming experiment which begins in 2015. Total sulfur and sulfur speciation were measured in peat cores (solid phase) from nine plots (hollows and hummocks) to a depth of 2 m. Peat samples were packed under nitrogen and frozen in the field immediately after collection. All subsequent sample storage, handling, and processing were conducted under inert gas. Sulfur speciation was measured using bulk sulfur 1s X-ray absorption near edge structure (XANES) spectroscopy at the SXRMB instrument at the Canadian Light Source, Saskatoon, SK, Canada and at the 9-BM instrument, Advanced Photon Source, Argonne National Laboratory, IL, USA. Total sulfur concentrations ranged from 968 to 4077 mg sulfur / kg dry peat. Sulfur content increased with depth from 2 g sulfur / m2 in the 0-10 cm increment to a maximum value of 38 g sulfur / m2 in the 50-60 cm increment. These sulfur loadings produced high quality XANES spectra. The nine cores exhibited reproducible trends with depth in both total sulfur and specific sulfur species; however, variability in sulfur speciation was greatest in the top 40 cm. All sulfur detected within the peat solids was in an organic form. The most abundant sulfur species group was composed of organic mono-sulfide and thiol forms, representing approximately half of the total sulfur at all depths. Sulfonate and ester-sulfate species were 10-15 mol% of sulfur and exhibited low variability with depth. A subsurface maximum in organic di-sulfide was observed in the 20-30 cm depth increment, which is the transition zone between transiently oxidized acrotelm and permanently saturated anaerobic catotelm. Quantification of major sulfur pools is important for the SPRUCE experiment as they are likely to be indicators of changes in the oxidation-reduction (redox) status, and mercury methylation potential, of the peat in response to warming and enhanced carbon dioxide.

ISSUES RELATED TO SOLUTION CHEMISTRY IN MERCURY SAMPLING IMPINGERS

EPA Science Inventory

Analysis of mercury (Hg) speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hgo). Such methods incl...

Mayr, Dobzhansky, and Bush and the complexities of sympatric speciation in Rhagoletis

PubMed Central

Feder, Jeffrey L.; Xie, Xianfa; Rull, Juan; Velez, Sebastian; Forbes, Andrew; Leung, Brian; Dambroski, Hattie; Filchak, Kenneth E.; Aluja, Martin

2005-01-01

The Rhagoletis pomonella sibling species complex is a model for sympatric speciation by means of host plant shifting. However, genetic variation aiding the sympatric radiation of the group in the United States may have geographic roots. Inversions on chromosomes 1-3 affecting diapause traits adapting flies to differences in host fruiting phenology appear to exist in the United States because of a series of secondary introgression events from Mexico. Here, we investigate whether these inverted regions of the genome may have subsequently evolved to become more recalcitrant to introgression relative to collinear regions, consistent with new models for chromosomal speciation. As predicted by the models, gene trees for six nuclear loci mapping to chromosomes other than 1-3 tended to have shallower node depths separating Mexican and U.S. haplotypes relative to an outgroup sequence than nine genes residing on chromosomes 1-3. We discuss the implications of secondary contact and differential introgression with respect to sympatric host race formation and speciation in Rhagoletis, reconciling some of the seemingly dichotomous views of Mayr, Dobzhansky, and Bush concerning modes of divergence. PMID:15851672

Influence of the surface speciation on biofilm attachment to chalcopyrite by Acidithiobacillus thiooxidans.

PubMed

Lara, René H; García-Meza, J Viridiana; González, Ignacio; Cruz, Roel

2013-03-01

Surfaces of massive chalcopyrite (CuFeS2) electrodes were modified by applying variable oxidation potential pulses under growth media in order to induce the formation of different secondary phases (e.g., copper-rich polysulfides, S n(2-); elemental sulfur, S(0); and covellite, CuS). The evolution of reactivity (oxidation capacity) of the resulting chalcopyrite surfaces considers a transition from passive or inactive (containing CuS and S n(2-)) to active (containing increasing amounts of S(0)) phases. Modified surfaces were incubated with cells of sulfur-oxidizing bacteria (Acidithiobacillus thiooxidans) for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the density of cells attached to chalcopyrite surfaces, the structure of the formed biofilm, and their exopolysaccharides and nucleic acids were analyzed by confocal laser scanning microscopy (CLSM) and scanning electron microscopy coupled to dispersive X-ray analysis (SEM-EDS). Additionally, CuS and S n(2-)/S(0) speciation, as well as secondary phase evolution, was carried out on biooxidized and abiotic chalcopyrite surfaces using Raman spectroscopy and SEM-EDS. Our results indicate that oxidized chalcopyrite surfaces initially containing inactive S n(2-) and S n(2-)/CuS phases were less colonized by A. thiooxidans as compared with surfaces containing active phases (mainly S(0)). Furthermore, it was observed that cells were partially covered by CuS and S(0) phases during biooxidation, especially at highly oxidized chalcopyrite surfaces, suggesting the innocuous effect of CuS phases during A. thiooxidans performance. These results may contribute to understanding the effect of the concomitant formation of refractory secondary phases (as CuS and inactive S n(2-)) during the biooxidation of chalcopyrite by sulfur-oxidizing microorganisms in bioleaching systems.

Speciation within Columnea section Angustiflora (Gesneriaceae): islands, pollinators and climate.

PubMed

Schulte, Lacie J; Clark, John L; Novak, Stephen J; Jeffries, Shandra K; Smith, James F

2015-03-01

Despite many advances in evolutionary biology, understanding the proximate mechanisms that lead to speciation for many taxonomic groups remains elusive. Phylogenetic analyses provide a means to generate well-supported estimates of species relationships. Understanding how genetic isolation (restricted gene flow) occurred in the past requires not only a well-supported molecular phylogenetic analysis, but also an understanding of when character states that define species may have changed. In this study, phylogenetic trees resolve species level relationships for fourteen of the fifteen species within Columnea section Angustiflorae (Gesneriaceae). The distributions of sister species pairs are compared and ancestral character states are reconstructed using Bayesian stochastic mapping. Climate variables were also assessed and shifts in ancestral climate conditions were mapped using SEEVA. The relationships between morphological character states and climate variables were assessed with correlation analyses. These results indicate that species in section Angustiflorae have likely diverged as a result of allopatric, parapatric, and sympatric speciation, with both biotic and abiotic forces driving morphological and phenological divergence. Copyright © 2015 Elsevier Inc. All rights reserved.

The Importance of pH, Oxygen, and Bitumen on the Oxidation and Precipitation of Fe(III)-(oxy)hydroxides during Hydraulic Fracturing of Oil/Gas Shales

NASA Astrophysics Data System (ADS)

Jew, A. D.; Dustin, M. K.; Harrison, A. L.; Joe-Wong, C. M.; Thomas, D.; Maher, K.; Brown, G. E.; Bargar, J.

2016-12-01

Due to the rapid growth of hydraulic fracturing in the United States, understanding the cause for the rapid production drop off of new wells over the initial months of production is paramount. One possibility for the production decrease is pore occlusion caused by the oxidation of Fe(II)-bearing phases resulting in Fe(III) precipitates. To understand the release and fate of Fe in the shale systems, we reacted synthesized fracture fluid at 80oC with shale from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.). A variety of wet chemical and synchrotron-based techniques (XRF mapping and x-ray absorption spectroscopy) were used to understand Fe release and solid phase Fe speciation. Solution pH was found to be the greatest factor for Fe release. Carbonate-poor Barnett and Marcellus shale showed rapid Fe release into solution followed by a plateau or significant drop in Fe concentrations indicating mineral precipitation. Conversely, in high carbonate shales, Eagle Ford and Green River, no Fe was detected in solution indicating fast Fe oxidation and precipitation. For all shale samples, bulk Fe EXAFS data show that a significant amount of Fe in the shales is bound directly to organic carbon. Throughout the course of the experiments inorganic Fe(II) phases (primarily pyrite) reacted while Fe(II) bound to C showed no indication of reaction. On the micron scale, XRF mapping coupled with μ-XANES spectroscopy showed that at pH < 4.0, Fe(III) bearing phases precipitated as diffuse surface precipitates of ferrihydrite, goethite, and magnetite away from Fe(II) point sources. In near circum-neutral pH systems, Fe(III)-bearing phases (goethite and hematite) form large particles 10's of μm's in diameter near Fe(II) point sources. Idealized systems containing synthesized fracturing fluid, dissolved ferrous chloride, and bitumen showed that bitumen released during reaction with fracturing fluids is capable of oxidizing Fe(II) to Fe(III) at pH's 2.0 and 7.0. This indicates that bitumen can play a large role in Fe oxidation and speciation in the subsurface. This work shows that shale mineralogy has a significant impact on the morphology and phases of Fe(III) precipitates in the subsurface which in turn can significantly impact subsurface solution flow.

Geochemical Weathering Increases Lead Bioaccessibility in Semi-Arid Mine Tailings

PubMed Central

Hayes, Sarah M.; Webb, Sam M.; Bargar, John R.; O'Day, Peggy A.; Maier, Raina M.; Chorover, Jon

2012-01-01

Mine tailings can host elevated concentrations of toxic metal(loid)s that represent a significant hazard to surrounding communities and ecosystems. Eolian transport, capable of translocating small (micrometer-sized) particles, can be the dominant mechanism of toxic metal dispersion in arid or semi-arid landscapes. Human exposure to metals can then occur via direct inhalation or ingestion of particulates. The fact that measured doses of total lead (Pb) in geomedia correlate poorly with blood Pb levels highlights a need to better resolve the precise distribution of molecularly-speciated metal-bearing phases in the complex particle mixtures. Species distribution controls bioaccessibility, thereby directly impacting health risk. This study seeks to correlate Pb-containing particle size and mineral composition with lability and bioaccessibility in mine tailings subjected to weathering in a semi-arid environment. We employed X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), coupled with sequential chemical extractions, to study Pb speciation in tailings from the semi-arid Arizona Klondyke State Superfund Site. Representative samples ranging in pH from 2.6 to 5.4 were selected for in-depth study of Pb solid-phase speciation. The principle lead-bearing phase was plumbojarosite (PbFe6(SO4)4(OH)12), but anglesite (PbSO4) and iron oxide-sorbed Pb were also observed. Anglesite, the most bioavailable mineral species of lead identified in this study, was enriched in surficial tailings samples, where Pb concentrations in the clay size fraction were 2–3 times higher by mass relative to bulk. A mobile and bioaccessible Pb phase accumulates in surficial tailings, with a corresponding increase in risk of human exposure to atmospheric particles. PMID:22553941

Organic Exudates Enhance Iron Bioavailability to Trichodesmium (IMS101) by Modifying Fe Speciation

NASA Astrophysics Data System (ADS)

Tohidi Farid, H.; Rose, A.; Schulz, K.

2016-02-01

Although ferrous iron (Fe (II)) is believed to be the most readily absorbed form of Fe by cells, under alkaline and oxygenated conditions typical of marine environments, the thermodynamically stable Fe(III) state dominates. In marine environments, this Fe(III) is primarily presents as organic Fe(III)L complexes whose bioavailability is highly variable. However, it has been demonstrated that some eukaryotic marine algae are able to release organic ligands into their surrounding environments that change Fe bioavailability through complexation and/or redox reactions. Nevertheless, it is unclear how Fe(II) oxidation and Fe(III) reduction rates might be modified by these exudates and how this might increase or decrease iron bioavailability to microorganisms. Here, the role of natural organic ligands excreted by the cyanobacterium Trichodesmium erythraeum on the oxidation kinetics of Fe(II) was studied using the luminol chemiluminescence technique. The oxidation kinetics of Fe(II) were examined at nanomolar Fe concentrations in presence of different concentrations of EDTA and dissolved organic carbon exuded by Trichodesmium cells. The results indicated that an increase in the concentration of exuded organic matter, and consequently L:Fe(II) ratio, resulted in decreasing rates of Fe(II) oxidation by oxygen, primarily due to formation of Fe(II) complexes. Moreover, the results demonstrated that the exudates from Trichodesmium may be able to reduce Fe(III) to the more bioavailable Fe(II) state under some circumstances. This study therefore supports the ability of microorganisms to manipulate Fe bioavailability by releasing organic compounds into the extracellular environment that retard Fe(II) oxidation rates or reducing Fe(III) species to Fe(II). It also provides new insight into the potential mechanism(s) by which Trichdesmium may acquire Fe under conditions where Fe bioavailability is otherwise limited.

Microbial Fe biomineralization in mafic and ultramafic rocks

NASA Astrophysics Data System (ADS)

Templeton, A. S.; Mayhew, L.; McCollom, T.; Trainor, T.

2011-12-01

Fluid-filled microfractures within mafic and ultramafic rocks, such as basalt and peridotite, may be one of the most ubiquitous microbial habitats on the modern and ancient earth. In seafloor and subseafloor systems, one of the dominant energy sources is the oxidation of Fe by numerous potential oxidants under aerobic to anaerobic conditions. In particular, the oxidation of Fe may be directly catalyzed by microbial organisms, or result in the production of molecular hydrogen which can then fuel diverse lithotrophic metabolisms. However, it remains challenging to identify the dominant metabolic activities and unravel the microscale biogeochemical processes occuring within such rock-hosted systems. We are investigating the mechanisms of solid-state Fe-oxidation and biomineralization in basalt, olivine, pyroxenes and basalts, in the presence and absence of microbial organisms that can thrive across the full stability range of water. In this talk we will present synchrotron-based x-ray scattering and spectroscopic analyses of Fe speciation within secondary minerals formed during microbially-mediated vs. abiotic water-rock interactions. Determining the valence state and mineralogy of Fe-bearing phases is critical for determining the water-rock reaction pathways and identifying potential biominerals that may form; therefore, we will highlight new approaches for identifying key Fe transformations within complex geological media. In addition, many of our experimental studies involve the growth of lithotrophic biofilms on well-characterized mineral surfaces in order to determine the chemistry of the microbe-mineral interface during progressive electron-transfer reactions. By coupling x-ray spectroscopy, x-ray diffraction, and electron-microscopy measurements, we will also contrast the evolution of mineral surfaces that undergo microbially-mediated oxidative alteration against minerals surfaces that produce H2 to sustain anaerobic microbial communities.

Size-separated particle fractions of stainless steel welding fume particles - A multi-analytical characterization focusing on surface oxide speciation and release of hexavalent chromium.

PubMed

Mei, N; Belleville, L; Cha, Y; Olofsson, U; Odnevall Wallinder, I; Persson, K-A; Hedberg, Y S

2018-01-15

Welding fume of stainless steels is potentially health hazardous. The aim of this study was to investigate the manganese (Mn) and chromium (Cr) speciation of welding fume particles and their extent of metal release relevant for an inhalation scenario, as a function of particle size, welding method (manual metal arc welding, metal arc welding using an active shielding gas), different electrodes (solid wires and flux-cored wires) and shielding gases, and base alloy (austenitic AISI 304L and duplex stainless steel LDX2101). Metal release investigations were performed in phosphate buffered saline (PBS), pH 7.3, 37°, 24h. The particles were characterized by means of microscopic, spectroscopic, and electroanalytical methods. Cr was predominantly released from particles of the welding fume when exposed in PBS [3-96% of the total amount of Cr, of which up to 70% as Cr(VI)], followed by Mn, nickel, and iron. Duplex stainless steel welded with a flux-cored wire generated a welding fume that released most Cr(VI). Nano-sized particles released a significantly higher amount of nickel compared with micron-sized particle fractions. The welding fume did not contain any solitary known chromate compounds, but multi-elemental highly oxidized oxide(s) (iron, Cr, and Mn, possibly bismuth and silicon). Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

GEOCHEMICAL MODELING OF ARSENIC SPECIATION AND MOBILIZATION: IMPLICATIONS FOR BIOREMEDIATION

EPA Science Inventory

Geochemical modeling techniques were used to examine the biogeochemical linkages between Fe, S, and As in shallow alluvial aquifers. We modeled: 1) the adsorption and desorption of As on the surface of hydrous ferric oxides (HFO’s) in stream beds under aerobic conditions; 2) red...

Investigation Of A Mercury Speciation Technique For Flue Gas Desulfurization Materials

EPA Science Inventory

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to bene...

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

NASA Technical Reports Server (NTRS)

Shock, Everett L.

1998-01-01

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Enhanced Oxidation of Isoprene and Monoterpenes in High and Low NOx Conditions

NASA Astrophysics Data System (ADS)

Tokarek, T. W.; Gilman, J.; Lerner, B. M.; Koss, A.; Yuan, B.; Taha, Y. M.; Osthoff, H. D.; Warneke, C.; De Gouw, J. A.

2015-12-01

In the troposphere, the photochemical oxidation of volatile organic compounds (VOCs) is primarily initiated by their reactions with the hydroxyl radical (OH) which yields peroxy radicals (HO2 and RO2). Concentrations of OH and the rates of VOC oxidation depend on the efficiency of peroxy radical recycling to OH. Radical recycling mainly occurs through reaction of HO2 with NO to produce NO2 and, ultimately, ozone (O3). Hence, the rate of VOC oxidation is dependent on NOx (=NO+NO2) concentration. The Shale Oil and Natural Gas Nexus (SONGNEX) campaign was conducted from March 17 to April 29, 2015 with the main goal of identifying and quantifying industrial sources of pollutants throughout the United States, in particular those associated with the production of oil and natural gas. In this work, a case study of biogenic VOC oxidation within and outside a power plant plume in the Haynesville basin near the border of Texas and Louisiana is presented. Isoprene, monoterpenes and their oxides were measured by H3O+ chemical ionization mass spectrometry (H3O+ CIMS) in high time resolution (1 s). Further, an improved Whole Air Sampler (iWAS) was used to collect samples for post-flight analysis by gas chromatography mass spectrometric detection (GC-MS) and yielded speciated quantification of biogenic VOCs. The monoterpene oxide to monoterpene ratio follows the spatial extent of the plume as judged by another tracer (NOx), tracking the enhancement of oxidation rates by NOx. The observations are rationalized with the aid of box modeling using the Master Chemical Mechanism (MCM).

Spatial and seasonal patterns in urban influence on regional concentrations of speciated aerosols across the United States

NASA Astrophysics Data System (ADS)

Hand, J. L.; Schichtel, B. A.; Malm, W. C.; Pitchford, M.; Frank, N. H.

2014-11-01

Monthly, seasonal, and annual mean estimates of urban influence on regional concentrations of major aerosol species were computed using speciated aerosol data from the rural IMPROVE network (Interagency Monitoring of Protected Visual Environments) and the United States Environmental Protection Agency's urban Chemical Speciation Network for the 2008 through 2011 period. Aggregated for sites across the continental United States, the annual mean and one standard error in urban excess (defined as the ratio of urban to nearby rural concentrations) was highest for elemental carbon (3.3 ± 0.2), followed by ammonium nitrate (2.5 ± 0.2), particulate organic matter (1.78 ± 0.08), and ammonium sulfate (1.23 ± 0.03). The seasonal variability in urban excess was significant for carbonaceous aerosols and ammonium nitrate in the West, in contrast to the low seasonal variability in the urban influence of ammonium sulfate. Generally for all species, higher excess values in the West were associated with localized urban sources while in the East excess was more regional in extent. In addition, higher excess values in the western United States in winter were likely influenced not only by differences in sources but also by combined meteorological and topographic effects. This work has implications for understanding the spatial heterogeneity of major aerosol species near the interface of urban and rural regions and therefore for designing appropriate air quality management strategies. In addition, the spatial patterns in speciated mass concentrations provide constraints for regional and global models.

Speciation and leachability of copper in mine tailings from porphyry copper mining: influence of particle size.

PubMed

Hansen, Henrik K; Yianatos, Juan B; Ottosen, Lisbeth M

2005-09-01

Mine tailing from the El Teniente-Codelco copper mine situated in VI Region of Chile was analysed in order to evaluate the mobility and speciation of copper in the solid material. Mine tailing was sampled after the rougher flotation circuits, and the copper content was measured to 1150 mg kg (-1) dry matter. This tailing was segmented into fractions of different size intervals: 0-38, 38-45, 45-53, 53-75, 75-106, 106-150, 150-212, and >212 microm, respectively. Copper content determination, sequential chemical extraction, and desorption experiments were carried out for each size interval in order to evaluate the speciation of copper. It was found that the particles of smallest size contained 50-60% weak acid leachable copper, whereas only 32% of the copper found in largest particles could be leached in weak acid. Copper oxides and carbonates were the dominating species in the smaller particles, and the larger particles contained considerable amounts of sulphides.

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments.

PubMed

Zhong, Huan; Wang, Wen-Xiong

2008-01-01

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.

Automation of liquid-liquid extraction-spectrophotometry using prolonged pseudo-liquid drops and handheld CCD for speciation of Cr(VI) and Cr(III) in water samples.

PubMed

Chen, Wen; Zhong, Guanping; Zhou, Zaide; Wu, Peng; Hou, Xiandeng

2005-10-01

A simple spectrophotometric system, based on a prolonged pseudo-liquid drop device as an optical cell and a handheld charge coupled device (CCD) as a detector, was constructed for automatic liquid-liquid extraction and spectrophotometric speciation of trace Cr(VI) and Cr(III) in water samples. A tungsten halogen lamp was used as the light source, and a laboratory-constructed T-tube with two open ends was used to form the prolonged pseudo-liquid drop inside the tube. In the medium of perchloric acid solution, Cr(VI) reacted with 1,5-diphenylcarbazide (DPC); the formed complex was automatically extracted into n-pentanol, with a preconcentration ratio of about 5. The organic phase with extracted chromium complex was then pumped through the optical cell for absorbance measurement at 548 nm. Under optimal conditions, the calibration curve was linear in the range of 7.5 - 350 microg L(-1), with a correlation coefficient of 0.9993. The limit of detection (3sigma) was 7.5 microg L(-1). That Cr(III) species cannot react with DPC, but can be oxidized to Cr(VI) prior to determination, is the basis of the speciation analysis. The proposed speciation analysis was sensitive, yet simple, labor-effective, and cost-effective. It has been preliminarily applied for the speciation of Cr(VI) and Cr(III) in spiked river and tap water samples. It can also be used for other automatic liquid-liquid extraction-spectrophotometric determinations.

A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atef, Nour; Kukkadapu, Goutham; Mohamed, Samah Y.

Iso-Octane (2,2,4-trimethylpentane) is a primary reference fuel and an important component of gasoline fuels. Furthermore, it is a key component used in surrogates to study the ignition and burning characteristics of gasoline fuels. This paper presents an updated chemical kinetic model for iso-octane combustion. Specifically, the thermodynamic data and reaction kinetics of iso-octane have been re-assessed based on new thermodynamic group values and recently evaluated rate coefficients from the literature. The adopted rate coefficients were either experimentally measured or determined by analogy to theoretically calculated values. New alternative isomerization pathways for peroxy-alkyl hydroperoxide (more » $$\\dot{O}$$OQOOH) radicals were added to the reaction mechanism. The updated kinetic model was compared against new ignition delay data measured in rapid compression machines (RCM) and a high-pressure shock tube. Our experiments were conducted at pressures of 20 and 40 atm, at equivalence ratios of 0.4 and 1.0, and at temperatures in the range of 632–1060 K. The updated model was further compared against shock tube ignition delay times, jet-stirred reactor oxidation speciation data, premixed laminar flame speeds, counterflow diffusion flame ignition, and shock tube pyrolysis speciation data available in the literature. Finally, the updated model was used to investigate the importance of alternative isomerization pathways in the low temperature oxidation of highly branched alkanes. When compared to available models in the literature, the present model represents the current state-of-the-art in fundamental thermochemistry and reaction kinetics of iso-octane; and thus provides the best prediction of wide ranging experimental data and fundamental insights into iso-octane combustion chemistry.« less

A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics

DOE PAGES

Atef, Nour; Kukkadapu, Goutham; Mohamed, Samah Y.; ...

2017-02-05

Iso-Octane (2,2,4-trimethylpentane) is a primary reference fuel and an important component of gasoline fuels. Furthermore, it is a key component used in surrogates to study the ignition and burning characteristics of gasoline fuels. This paper presents an updated chemical kinetic model for iso-octane combustion. Specifically, the thermodynamic data and reaction kinetics of iso-octane have been re-assessed based on new thermodynamic group values and recently evaluated rate coefficients from the literature. The adopted rate coefficients were either experimentally measured or determined by analogy to theoretically calculated values. New alternative isomerization pathways for peroxy-alkyl hydroperoxide (more » $$\\dot{O}$$OQOOH) radicals were added to the reaction mechanism. The updated kinetic model was compared against new ignition delay data measured in rapid compression machines (RCM) and a high-pressure shock tube. Our experiments were conducted at pressures of 20 and 40 atm, at equivalence ratios of 0.4 and 1.0, and at temperatures in the range of 632–1060 K. The updated model was further compared against shock tube ignition delay times, jet-stirred reactor oxidation speciation data, premixed laminar flame speeds, counterflow diffusion flame ignition, and shock tube pyrolysis speciation data available in the literature. Finally, the updated model was used to investigate the importance of alternative isomerization pathways in the low temperature oxidation of highly branched alkanes. When compared to available models in the literature, the present model represents the current state-of-the-art in fundamental thermochemistry and reaction kinetics of iso-octane; and thus provides the best prediction of wide ranging experimental data and fundamental insights into iso-octane combustion chemistry.« less

Probing Selenium-Ion Distributions and Changes in Redox-State at Biofilm/Mineral Interfaces by Coupling Long-period X-ray Standing Wave and XANES Measurements

NASA Astrophysics Data System (ADS)

Templeton, A. S.; Trainor, T. P.; Spormann, A. M.; Brown, G. E.

2002-12-01

Metal sorption and precipitation reactions at biological as well as mineral surfaces are important controls on metal speciation and bioavailability in natural environments. When highly hydrated biofilms form on mineral surfaces, numerous competitive and synergistic effects are predicted to occur. Experimentally, it is challenging to determine where the sorbed metal ions are localized, the relative affinity of the biological vs. mineral surface sites, or to monitor biomineralization reactions or changes in metal speciation that may also occur. A large part of the difficulty is due to the low concentrations of sorbed ions, the small length-scale of the biofilm-mineral interface, and the complex interplay between microbially-catalayzed redox transformations vs. sorption and/or transport processes. Long-period x-ray standing wave (XSW) techniques are well-suited to determining the vertical distribution of metal(oid) species within biofilms overlying mineral surfaces. We will discuss experiments where Se fluorescence yield profiles are used to compare the affinity of Burkholderia cepacia biofilms for binding Se(IV) and Se(VI) species relative to underlying alpha-Al2O3 substrates over three orders of magnitude in [Se]. In addition, we will discuss how coupling the XSW experiments to grazing-incidence, spatially-resolved Se K-edge XANES spectroscopy can be used to differentiate between the oxidation state of the Se complexes localized within the biofilm vs. the mineral surface. This approach is used to monitor changes in the relative distributions of Se(VI), Se(IV) and Se(0) species as a function of time and proximity to the mineral surface. The long-period XSW data show that selenite preferentially binds to the oxide surfaces, particularly at low [Se]. When B. cepacia is metabolically active, B. cepacia rapidly reduces a fraction of the Se(IV) to the red elemental Se form. In contrast, selenate is preferentially partitioned into the B. cepacia biofilms at all [Se] tested due to a lower affinity for binding to the mineral surface. XANES spectra show that rapid reduction of selenate by B. cepacia to Se(IV) and Se(0) species subsequently results in a vertical segregation of Se species at the B. cepacia/alpha-Al2O3 interface. Elemental Se accumulates within the biofilm with the Se(VI), whereas selenite intermediates preferentially sorb to the underlying oxide surface.

Speciation at the Mogollon Rim in the Arizona Mountain Kingsnake (Lampropeltis pyromelana).

PubMed

Burbrink, Frank T; Yao, Helen; Ingrasci, Matthew; Bryson, Robert W; Guiher, Timothy J; Ruane, Sara

2011-09-01

Studies of speciation and taxon delimitation are usually decoupled. Combining these methods provides a stronger theoretical ground for recognizing new taxa and understanding processes of speciation. Using coalescent methods, we examine speciation, post-speciation population demographics, and taxon delimitation in the Arizona Mountain Kingsnake (Lampropeltis pyromelana), a species restricted to high elevations in southwestern United States and northern Mexico (SW). These methods provide a solid foundation for understanding how biogeographic barriers operate at the regional scale in the SW. Bayesian species delimitation methods, using three loci from samples of L. pyromelana taken throughout their range, show strong support for the existence of two species that are separated by low elevation habitats found between the Colorado Plateau/ Mogollon Rim and the Sierra Madre Occidental. Our results suggest an allopatric mode of speciation given the near absence of gene flow over time, which resulted in two lineages of unequal population sizes. Speciation likely occurred prior to the Pleistocene, during the aridification of the SW and/or the uplift of the Colorado Plateau, and while these species occupy similar high-elevation niches, they are isolated by xeric conditions found in the intervening low deserts. Furthermore, post-speciation demographics suggest that populations of both lineages were not negatively impacted by climate change throughout the Pleistocene. Finally, our results suggest that at least for this group, where divergence is old and gene flow is low, Bayesian species delimitation performs well. Copyright © 2011 Elsevier Inc. All rights reserved.

Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

EPA Science Inventory

Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

BIOGEOCHEMICAL PROCESSES CONTROLLING ARSENIC SPECIATION AND BIOTRANSFORMATION IN GRANULAR FERRIC HYDROXIDE COATED SAND

EPA Science Inventory

Arsenic mobilization from solid phase Fe (III) hydroxides is an issue of concern, as water-borne arsenic can migrate into pristine environments, endangering aquatic and human life. In general, metal oxide (hydroxides) exerts a dominating effect on the fate and transport of arseni...

CD SPECIATION ASSOCIATED WITH IRON OXIDES AND BIOSOLIDS

EPA Science Inventory

The environmental impact and potential hazards of metals in biosolids to plants, animals and the human food chain have been studied for decades. From this body of work, it has been concluded the addition of biosolids to the soil alters the chemical phases in the soil system beyon...

INVESTIGATING OXIDATION MECHANISMS OF HGO IN THE FREE TROPOSPHERE AND ITS INFLUENCE ON LONG RANGE MERCURY TRANSPORT

EPA Science Inventory

ORD initiated automated speciated mercury measurements at the NOAA Mauna Loa Observatory (MLO), a high altitude research station (~11,500 feet) in 2001. Mercury monitoring at MLO was supplemented with trace element aerosol, criteria gas, and gas and particulate halide measurement...

Iron Drinking Water Pipe Corrosion Products: Concentrators of Toxic Metals

DTIC Science & Technology

2013-01-01

health risk. In addition Pb corrosion products may be sinks for other metals such as chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn). These...Vanadium K-Edge X-ray Absorption Near-Edge Structure Interpretation: Application to the Speciation of Vanadium in Oxide Phases from Steel Slag ’, Journal

INVESTIGATION OF SELECTIVE CATALYTIC REDUCTION IMPACT ON MERCURY SPECIATION UNDER SIMULATED NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

Selective catalytic reduction (SCR) technology is being increasingly applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury in the coal com...

Speciation and bioavailability of some heavy metals in agricultural soils used for cultivating various vegetables in Bedugul, Bali

NASA Astrophysics Data System (ADS)

Siaka, I. Made; Utama, I. Made Supartha; Manuaba, I. B. Putra; Adnyana, I. Made; Sahara, Emmy

2016-03-01

This paper discusses the speciation and bioavailability of some heavy metals in agricultural soils used to cultivate various vegetables in Bedugul, Bali. Vegetables grown on contaminated soils where agrochemicals were applied uncontrolled could contain a number of heavy metals. This could occur in the vegetables produced from agricultural soils of Bedugul as the farmers applied agrochemicals excessively. In considering the metals transport to the vegetables, a speciation and bioavailability methods were necessary to be studied. Wet digestion and sequential extraction techniques were employed to the sample prior to the metals measurement by AAS. The results showed that the average concentrations of Pb, Cu, Cd, Cr, and Zn in the soils were 38.531, 132.126, 7.689, 15.952, and 147.275 mg/kg, respectively. The highest concentrations of Pb and Zn were found in the soil for cultivating lettuce, Cd and Cr in the soil for tomato, and Cu in the soil for potatoes. It was found that the speciation of Pb, Cu, Cd, and Cr were predominantly bound to Fe-Mn oxides fraction, while Zn was mostly associated with the EFLE (easily, freely, leachable, and exchangeable) fractions. The highest bioavailability among the metals in the studied soils was Cr, while the lowest was Cu.

Metal Speciation in Landfill Leachates with a Focus on the Influence of Organic Matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

F Claret; C Tournassat; C Crouzet

This study characterizes the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc aremore » super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2002-01-01

The distribution of inorganic arsenic species must be preserved in the field to eliminate changes caused by metal oxyhydroxide precipitation, photochemical oxidation, and redox reactions. Arsenic species sorb to iron and manganese oxyhydroxide precipitates, and arsenite can be oxidized to arsenate by photolytically produced free radicals in many sample matrices. Several preservatives were evaluated to minimize metal oxyhydroxide precipitation, such as inorganic acids and ethylenediaminetetraacetic acid (EDTA). EDTA was found to work best for all sample matrices tested. Storing samples in opaque polyethylene bottles eliminated the effects of photochemical reactions. The preservation technique was tested on 71 groundwater and six acid mine drainage samples. Concentrations in groundwater samples reached 720 ??g-As/L for arsenite and 1080 ??g-As/L for arsenate, and acid mine drainage samples reached 13 000 ??g-As/L for arsenite and 3700 ??g-As/L for arsenate. The arsenic species distribution in the samples ranged from 0 to 90% arsenite. The stability of the preservation technique was established by comparing laboratory arsenic speciation results for samples preserved in the field to results for subsamples speciated onsite. Statistical analyses indicated that the difference between arsenite and arsenate concentrations for samples preserved with EDTA in opaque bottles and field speciation results were analytically insignificant. The percentage change in arsenite:arsenate ratios for a preserved acid mine drainage sample and groundwater sample during a 3-month period was -5 and +3%, respectively.

Thermal reactions of uranium metal, UO 2, U 3O 8, UF 4, and UO 2F 2 with NF 3 to produce UF 6

NASA Astrophysics Data System (ADS)

McNamara, Bruce; Scheele, Randall; Kozelisky, Anne; Edwards, Matthew

2009-11-01

This paper demonstrates that NF 3 fluorinates uranium metal, UO 2, UF 4, UO 3, U 3O 8, and UO 2F 2·2H 2O to produce the volatile UF 6 at temperatures between 100 and 550 °C. Thermogravimetric and differential thermal analysis reaction profiles are described that reflect changes in the uranium fluorination/oxidation state, physiochemical effects, and instances of discrete chemical speciation. Large differences in the onset temperatures for each system investigated implicate changes in mode of the NF 3 gas-solid surface interaction. These studies also demonstrate that NF 3 is a potential replacement fluorinating agent in the existing nuclear fuel cycle and in actinide volatility reprocessing.

EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolery, T.J.

1992-09-14

EQ3NR is an aqueous solution speciation-solubility modeling code. It is part of the EQ3/6 software package for geochemical modeling. It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations which describe the thermodynamic activity coefficients of these species. The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, pHCl, Eh, pe, and oxygen fugacity. The input may also include a desiredmore » electrical balancing adjustment and various constraints which impose equilibrium with special pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities). The code evaluates the degree of disequilibrium in terms of the saturation index (SI = 1og Q/K) and the thermodynamic affinity (A = {minus}2.303 RT log Q/K) for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself. Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples. Equilibrium fugacities are computed for gas species. The code is highly flexible in dealing with various parameters as either model inputs or outputs. The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.« less

Influence of organic substrates on the kinetics of bacterial As(III) oxidation

NASA Astrophysics Data System (ADS)

Lescure, T.; Joulian, C.; Bauda, P.; Hénault, C.; Battaglia-Brunet, F.

2012-04-01

Soil microflora plays a major role on the behavior of metals and metalloids. Arsenic speciation, in particular, is related to the activity of bacteria able to oxidize, reduce or methylate this element, and determines mobility, bioavailability and toxicity of As. Arsenite (AsIII) is more toxic and more mobile than arsenate (AsV). Bacterial As(III)-oxidation tends to reduce the toxicity of arsenic in soils and the risk of transfer toward underlying aquifers, that would affect the quality of water resources. Previous results suggest that organic matter may affect kinetics or efficiency of bacterial As(III)-oxidation in presence of oxygen, thus in conventional physico-chemical conditions of a surface soil. Different hypothesis can be proposed to explain the influence of organic matter on As(III) oxidation. Arsenic is a potential energy source for bacteria. The presence of easily biodegradable organic matter may inhibit the As(III) oxidation process because bacteria would first metabolize these more energetic substrates. A second hypothesis would be that, in presence of organic matter, the Ars system involved in bacterial resistance to arsenic would be more active and would compete with the Aio system of arsenite oxidation, decreasing the global As(III) oxidation rate. In addition, organic matter influences the solubility of iron oxides which often act as the main pitfalls of arsenic in soils. The concentration and nature of organic matter could therefore have a significant influence on the bioavailability of arsenic and hence on its environmental impact. The influence of organic matter on biological As(III) oxidation has not yet been determined in natural soils. In this context, soil amendment with organic matter during operations of phytostabilization or, considering diffuse pollutions, through agricultural practices, may affect the mobility and bio-availability of the toxic metalloid. The objective of the present project is to quantify the influence of organic matter on the bacterial speciation of arsenic in contaminated soils. Moreover, the biogeochemical consequences of this phenomenon on the mobility and ecotoxicity of this metalloid will be studied. The first task of this program is the precise and systematic investigation of the influence of different types and concentrations of organic matters on the activity of As(III)-oxidizing pure strains. Influence of aspartate, succinate (simple substrates) and yeast extract (complex substrate) on As(III)-oxidation kinetics has been studied. For each experiment, the bacterial growth and the expression of genes involved in the speciation of arsenic, i.e. aio and ars genes, has been monitored. A direct perspective of this work will be to perform experiments with humic and fulvic acids (complex organic matter commonly found in soils), and with water-extracted organic matter from polluted soils. Then the As(III)-oxidation activity of bacterial communities extracted from contaminated soils will be followed. These assays should allow the screening of conditions which will be applied in subsequent experiments with several real contaminated soils, including a former mining site, impacted industrial sites, and a forest soil heavily contaminated after arsenical ammunitions storage. This work is co-funded by BRGM and ADEME (convention TEZ 11-16).

Arsenite and Ferrous Iron Oxidation Linked to Chemolithotrophic Denitrification for the Immobilization of Arsenic in Anoxic Environments

PubMed Central

Sun, Wenjie; Sierra-Alvarez, Reyes; Milner, Lily; Oremland, Ron; Field, Jim A.

2014-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3− to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flow sand filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (SF1) or absence (SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 µg l−1 was reduced to 10.6 (±9.6) µg l−1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5–10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns was close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by XRD and XPS. The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxides coated sands with adsorbed As(V). PMID:19764221

Effects of manganese oxide-modified biochar composites on arsenic speciation and accumulation in an indica rice (Oryza sativa L.) cultivar.

PubMed

Yu, Zhihong; Qiu, Weiwen; Wang, Fei; Lei, Ming; Wang, Di; Song, Zhengguo

2017-02-01

A pot experiment was used to investigate arsenic (As) speciation and accumulation in rice, as well as its concentration in both heavily contaminated and moderately contaminated soils amended with manganese oxide-modified biochar composites (MBC) and biochar alone (BC). In heavily As-contaminated soil, application of BC and MBC improved the weight of above-ground part and rice root, whereas in moderately As-contaminated soil, the application of MBC and low rate BC amendment increased rice root, grain weight and the biomass of the plant. Arsenic reduction in different parts of rice grown in MBC-amended soils was greater than that in plants cultivated in BC-amended soils. Such reduction can be attributed to the oxidation of arsenite, As(III), to arsenate, As(V), by Mn-oxides, which also had a strong adsorptive capacity for As(V). MBC amended to As-contaminated soil had a positive effect on amino acids. The Fe and Mn levels in the iron-manganese plaque that formed on the rice root surface differed among the treatments. MBC addition significantly increased Mn content (p < 0.05); the application of 2.0% MBC increased Mn content 36- and 10-fold compared to the control in heavily and moderately As-contaminated soils, respectively. The results indicate that application of Mn oxide-modified biochar to As-contaminated paddy soil could effectively remediate contaminated soil and reduce As accumulation in edible parts of rice. Copyright © 2016 Elsevier Ltd. All rights reserved.

Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2013-09-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices including diesel particulate filters (DPF), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOC). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle, Urban Dynamometer Driving Schedule, and creep+idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photo-oxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary and secondary fine particulate matter from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after three hours of oxidation at typical urban VOC : NOx ratios (3:1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the non-methane organic gas emissions that could not be speciated using traditional one-dimensional gas-chromatography. The unspeciated organics - likely comprising less volatile species, such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep+idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

Dynamic coupled metal transport-speciation model: application to assess a zinc-contaminated lake.

PubMed

Bhavsar, Satyendra P; Diamond, Miriam L; Gandhi, Nilima; Nilsen, Joel

2004-10-01

A coupled metal transport and speciation/complexation model (TRANSPEC) has been developed to estimate the speciation and fate of multiple interconverting species in surface aquatic systems. Dynamic-TRANSPEC loosely, sequentially couples the speciation/complexation and fate modules that, for the unsteady state formulation, run alternatively at every time step. The speciation module first estimates species abundance using, in this version, MINEQL+ considering time-dependent changes in water and pore-water chemistry. The fate module is based on the quantitative water air sediment interaction (QWASI) model and fugacity/aquivalence formulation, with the option of using a pseudo-steady state solution to account for past discharges. Similarly to the QWASI model for organic contaminants, TRANSPEC assumes the instantaneous equilibrium distribution of metal species among dissolved, colloidal, and particulate phases based on ambient chemistry parameters that can be collected through conventional field methods. The model is illustrated with its application to Ross Lake (Manitoba, Canada) that has elevated Zn concentrations due to discharges over 70 years from a mining operation. Using measurements from field studies, the model reproduces year-round variations in Zn water concentrations. A 10-year projection for current conditions suggests decreasing Zn remobilization and export from the lake. Decreasing Zn loadings increases sediment-to-water transport but decreases water concentrations, and vice versa. Species distribution is affected by pH such that a decrease in pH increases metal export from the lake and vice versa.

Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles.

PubMed

Pidchenko, Ivan; Kvashnina, Kristina O; Yokosawa, Tadahiro; Finck, Nicolas; Bahl, Sebastian; Schild, Dieter; Polly, Robert; Bohnert, Elke; Rossberg, André; Göttlicher, Jörg; Dardenne, Kathy; Rothe, Jörg; Schäfer, Thorsten; Geckeis, Horst; Vitova, Tonya

2017-02-21

Uranium redox states and speciation in magnetite nanoparticles coprecipitated with U(VI) for uranium loadings varying from 1000 to 10 000 ppm are investigated by X-ray absorption spectroscopy (XAS). It is demonstrated that the U M 4 high energy resolution X-ray absorption near edge structure (HR-XANES) method is capable to clearly characterize U(IV), U(V), and U(VI) existing simultaneously in the same sample. The contributions of the three different uranium redox states are quantified with the iterative transformation factor analysis (ITFA) method. U L 3 XAS and transmission electron microscopy (TEM) reveal that initially sorbed U(VI) species recrystallize to nonstoichiometric UO 2+x nanoparticles within 147 days when stored under anoxic conditions. These U(IV) species oxidize again when exposed to air. U M 4 HR-XANES data demonstrate strong contribution of U(V) at day 10 and that U(V) remains stable over 142 days under ambient conditions as shown for magnetite nanoparticles containing 1000 ppm U. U L 3 XAS indicates that this U(V) species is protected from oxidation likely incorporated into octahedral magnetite sites. XAS results are supported by density functional theory (DFT) calculations. Further characterization of the samples include powder X-ray diffraction (pXRD), scanning electron microscopy (SEM) and Fe 2p X-ray photoelectron spectroscopy (XPS).

Plutonium interaction studies with the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99: changes in the plutonium speciation by solvent extractions.

PubMed

Moll, Henry; Cherkouk, Andrea; Bok, Frank; Bernhard, Gert

2017-05-01

Since plutonium could be released from nuclear waste disposal sites, the exploration of the complex interaction processes between plutonium and bacteria is necessary for an improved understanding of the fate of plutonium in the vicinity of such a nuclear waste disposal site. In this basic study, the interaction of plutonium with cells of the bacterium, Sporomusa sp. MT-2.99, isolated from Mont Terri Opalinus Clay, was investigated anaerobically (in 0.1 M NaClO 4 ) with or without adding Na-pyruvate as an electron donor. The cells displayed a strong pH-dependent affinity for Pu. In the absence of Na-pyruvate, a strong enrichment of stable Pu(V) in the supernatants was discovered, whereas Pu(IV) polymers dominated the Pu oxidation state distribution on the biomass at pH 6.1. A pH-dependent enrichment of the lower Pu oxidation states (e.g., Pu(III) at pH 6.1 which is considered to be more mobile than Pu(IV) formed at pH 4) was observed in the presence of up to 10 mM Na-pyruvate. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g., biosorption and bioreduction.

Theoretical Modeling of (99)Tc NMR Chemical Shifts.

PubMed

Hall, Gabriel B; Andersen, Amity; Washton, Nancy M; Chatterjee, Sayandev; Levitskaia, Tatiana G

2016-09-06

Technetium-99 (Tc) displays a rich chemistry due to its wide range of accessible oxidation states (from -I to +VII) and ability to form coordination compounds. Determination of Tc speciation in complex mixtures is a major challenge, and (99)Tc nuclear magnetic resonance (NMR) spectroscopy is widely used to probe chemical environments of Tc in odd oxidation states. However, interpretation of (99)Tc NMR data is hindered by the lack of reference compounds. Density functional theory (DFT) calculations can help to fill this gap, but to date few computational studies have focused on (99)Tc NMR of compounds and complexes. This work evaluates the effectiveness of both pure generalized gradient approximation and their corresponding hybrid functionals, both with and without the inclusion of scalar relativistic effects, to model the (99)Tc NMR spectra of Tc(I) carbonyl compounds. With the exception of BLYP, which performed exceptionally well overall, hybrid functionals with inclusion of scalar relativistic effects are found to be necessary to accurately calculate (99)Tc NMR spectra. The computational method developed was used to tentatively assign an experimentally observed (99)Tc NMR peak at -1204 ppm to fac-Tc(CO)3(OH)3(2-). This study examines the effectiveness of DFT computations for interpretation of the (99)Tc NMR spectra of Tc(I) coordination compounds in high salt alkaline solutions.

Surficial weathering of iron sulfide mine tailings under semi-arid climate.

PubMed

Hayes, Sarah M; Root, Robert A; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

2014-09-15

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg -1 , respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in the lowest pH samples, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s.

Surficial weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

2014-01-01

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130–140 and 100–120 g kg−1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in the lowest pH samples, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s. PMID:25197102

Surficial weathering of iron sulfide mine tailings under semi-arid climate

NASA Astrophysics Data System (ADS)

Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina M.; Chorover, Jon

2014-09-01

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering in a semi-arid climate at an EPA Superfund Site in central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg-1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in samples with the lowest pH, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s.

Modeling Non-Steady Isotopologue and Isotopomer Speciation and Fractionation during Denitrification in Soils

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2009-12-01

The composition and location of 15N atoms on N2O isotopomers and isotopologues during isotope speciation has been used to characterize soil biological N cycling and N2O surface emissions. Although there exist few experimental observations, no attempt has been made to model N2O isotopomer speciation. The mathematical treatment of biological kinetic reactions in isotopic applications normally makes use of first-order and quasi steady-state complexation assumptions without taking into account changes in enzyme concentration, reaction stoichiometry, and isotopologue and isotopomer speciation. When multiatomic isotopically-labeled reactants are used in a multi-molecurar reaction, these assumptions may fail since they always lead to a constant fractionation factor and cannot describe speciation of isotopologues and isotopomers. We have developed a mathematical framework that is capable of describing isotopologue and isotopmer speciation and fractionation under the assumption of non-steady complexation during biological kinetic reactions that overcome the limitations mentioned above. This framework was applied to a case study of non-steady (variable and inverse) isotopic effects observed during N2O production and consumption in soils. Our mathematical treatment has led to generalized kinetic equations which replicate experimental observations with high accuracy and help interpret non-steady isotopic effects and isotopologue and isotopomer speciation. The kinetic equations introduced and applied here have general validity in describing isotopic effects in any biochemical reactions by considering: changing enzyme concentrations, mass and isotope conservation, and reaction stoichiometry. The equations also describe speciation of any isotopologue and isotopomer product from any isotopologue and isotopmer reactant.

Current understanding of the driving mechanisms for spatiotemporal variations of atmospheric speciated mercury: a review

NASA Astrophysics Data System (ADS)

Mao, Huiting; Cheng, Irene; Zhang, Leiming

2016-10-01

Atmospheric mercury (Hg) is a global pollutant and thought to be the main source of mercury in oceanic and remote terrestrial systems, where it becomes methylated and bioavailable; hence, atmospheric mercury pollution has global consequences for both human and ecosystem health. Understanding of spatial and temporal variations of atmospheric speciated mercury can advance our knowledge of mercury cycling in various environments. This review summarized spatiotemporal variations of total gaseous mercury or gaseous elemental mercury (TGM/GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM) in various environments including oceans, continents, high elevation, the free troposphere, and low to high latitudes. In the marine boundary layer (MBL), the oxidation of GEM was generally thought to drive the diurnal and seasonal variations of TGM/GEM and GOM in most oceanic regions, leading to lower GEM and higher GOM from noon to afternoon and higher GEM during winter and higher GOM during spring-summer. At continental sites, the driving mechanisms of TGM/GEM diurnal patterns included surface and local emissions, boundary layer dynamics, GEM oxidation, and for high-elevation sites mountain-valley winds, while oxidation of GEM and entrainment of free tropospheric air appeared to control the diurnal patterns of GOM. No pronounced diurnal variation was found for Tekran measured PBM at MBL and continental sites. Seasonal variations in TGM/GEM at continental sites were attributed to increased winter combustion and summertime surface emissions, and monsoons in Asia, while those in GOM were controlled by GEM oxidation, free tropospheric transport, anthropogenic emissions, and wet deposition. Increased PBM at continental sites during winter was primarily due to local/regional coal and wood combustion emissions. Long-term TGM measurements from the MBL and continental sites indicated an overall declining trend. Limited measurements suggested TGM/GEM increasing from the Southern Hemisphere (SH) to the Northern Hemisphere (NH) due largely to the vast majority of mercury emissions in the NH, and the latitudinal gradient was insignificant in summer probably as a result of stronger meridional mixing. Aircraft measurements showed no significant vertical variation in GEM over the field campaign regions; however, depletion of GEM was observed in stratospherically influenced air masses. In examining the remaining questions and issues, recommendations for future research needs were provided, and among them is the most imminent need for GOM speciation measurements and fundamental understanding of multiphase redox kinetics.

Lead Speciation and In Vitro Bioaccessibility of Compost-Amended Urban Garden Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Attanayake, Chammi P.; Hettiarachchi, Ganga M.; Ma, Qing

In situ soil amendments can modify the Pb bioavailability by changing soil Pb speciation. Urban soils from three vegetable gardens containing different total Pb concentrations were used. The study evaluated how compost amendment and aging of soil-compost mixture in situ affected the following: (i) soil Pb speciation in the field and (ii) change of soil Pb speciation during an in vitro bioaccessibility extraction mimicking gastric phase dissolution at pH 2.5. X-ray absorption fine structure spectroscopy was used to determine Pb speciation in amended and nonamended soils and residues left after in vitro bioaccessibility extraction of those soils. Compost amendment andmore » aging of compost in the field had a negligible effect on Pb bioaccessibility in the soils. Major Pb species in the soils were Pb sorbed to Fe oxy(hydr)oxide (Pb-Fh) and to soil organic C (Pb-Org). The fraction of Pb-Org was increased as soil-compost mixture aged in the field. During the in vitro extraction, the fraction of Pb-Fh was decreased, the fraction of Pb-Org was increased, and hydroxypyromorphite was formed in both amended and nonamended soils. Freshly incorporated compost enhanced the dissolution of Pb-Fh during the extraction. As soil-compost mixture aged in the field, the dissolution of Pb-Fh was low, demonstrating more stability of the Pb-Fh during the extraction. Compost amendment showed potential to contribute to reduced bioaccessibility of Pb as compost aged in the soil by increasing Pb-Org fraction in the field and stability of Pb-Fh during the in vitro bioaccessibility extraction.« less

99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

PubMed

McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

2012-08-20

The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to make the π*(M═O) orbitals accessible to the addition of electrons. This result is consistent with previous extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) data that reveal that the Tc(V) is "pulled" into the -α1 framework and that may facilitate the reduction of Tc(V)O-α1 and stabilize lower Tc oxidation states. This study highlights the inequivalency of the two sites, and their impact on the chemical properties of the Tc substituted in these positions.

LINKING SOLID PHASE SPECIATION OF PB SEQUESTERED TO BIRNESSITE TO ORAL PB BIOACCESSIBLITY: IMPLICATIONS FOR SOIL REMEDIATION

EPA Science Inventory

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simula...

Analysis of Arsenicals and Their Sulfur Analogs in Biological Samples Using HPLC with Collision Cell ICP-MS and ESI-MS/MS

EPA Science Inventory

Recent arsenic speciation studies have indicated that the sulfur analogs of the more common arsenic oxides are present in environmental and biological systems. This discovery was previously impeded due to the strong affinity of these arsenic-sulfides for the stationary phases typ...

Rapid photooxidation of Sb(III) in the presence of different Fe(III) species

NASA Astrophysics Data System (ADS)

Kong, Linghao; He, Mengchang; Hu, Xingyun

2016-05-01

The toxicity and mobility of antimony (Sb) are strongly influenced by the redox processes associated with Sb. Dissolved iron (Fe) is widely distributed in the environment as different species and plays a significant role in Sb speciation. However, the mechanisms of Sb(III) oxidation in the presence of Fe have remained unclear because of the complexity of Fe and Sb speciation. In this study, the mechanisms of Sb(III) photooxidation in the presence of different Fe species were investigated systematically. The photooxidation of Sb(III) occurred over a wide pH range, from 1 to 10. Oxygen was not a predominant or crucial factor in the Sb(III) oxidation process. The mechanism of Sb(III) photooxidation varied depending on the Fe(III) species. In acidic solution (pH 1-3), dichloro radicals (radCl2-) and hydroxyl radicals (radOH) generated by the photocatalysis of FeCl2+ and FeOH2+ were the main oxidants for Sb(III) oxidation. Fe(III) gradually transformed into the colloid ferric hydroxide (CFH) and ferrihydrite in circumneutral and alkaline solutions (pH 4-10). Photooxidation of Sb(III) occurred through electron transfer from Sb(III) to Fe(III) along with the reduction of Fe(III) to Fe(II) through a ligand-to-metal charge-transfer (LMCT) process. The photocatalysis of different Fe(III) species may play an important role in the geochemical cycle of Sb(III) in surface soil and aquatic environments.

The speciation of soluble sulphur compounds in bacterial culture fluids by X-ray absorption near edge structure spectroscopy.

PubMed

Franz, Bettina; Lichtenberg, Henning; Hormes, Josef; Dahl, Christiane; Prange, Alexander

2009-11-01

Over the last decade X-ray absorption near edge structure (XANES) spectroscopy has been used in an increasing number of microbiological studies. In addition to other applications it has served as a valuable tool for the investigation of the sulphur globules deposited intra- or extracellularly by certain photo- and chemotrophic sulphur-oxidizing (Sox) bacteria. For XANES measurements, these deposits can easily be concentrated by filtration or sedimentation through centrifugation. However, during oxidative metabolism of reduced sulphur compounds, such as sulphide or thiosulphate, sulphur deposits are not the only intermediates formed. Soluble intermediates such as sulphite may also be produced and released into the medium. In this study, we explored the potential of XANES spectroscopy for the detection and speciation of sulphur compounds in culture supernatants of the phototrophic purple sulphur bacterium Allochromatium vinosum. More specifically, we investigated A. vinosum DeltasoxY, a strain with an in frame deletion of the soxY gene. This gene encodes an essential component of the thiosulphate-oxidizing Sox enzyme complex. Improved sample preparation techniques developed for the DeltasoxY strain allowed for the first time not only the qualitative but also the quantitative analysis of bacterial culture supernatants by XANES spectroscopy. The results thus obtained verified and supplemented conventional HPLC analysis of soluble sulphur compounds. Sulphite and also oxidized organic sulphur compounds were shown by XANES spectroscopy to be present, some of which were not seen when standard HPLC protocols were used.

Oxidation of octylphenol by ferrate(VI).

PubMed

Anquandah, George A K; Sharma, Virender K

2009-01-01

The rates of the oxidation of octylphenols (OP) by potassium ferrate(VI) (K(2)FeO(4)) in water were determined as a function of pH (8.0-10.9) at 25 degrees C. The rate law for the oxidation of OP by Fe(VI) was found to be first order with each reactant. The observed second-order rate constants, k(obs), for the oxidation of alkylphenols decreased with an increase in pH. The speciation of Fe(VI) (HFeO(4)(-) and FeO(4)(2 -)) and OP (OP-OH and OP-O(-)) species were used to determine individual rate constants of the reactions. Comparison of rate constants and half-lives of oxidation of OP by Fe(VI) with nonylphenol (NP) and bisphenol-A (BPA) were conducted to demonstrate that Fe(VI) efficiently oxidizes environmentally relevant alkylphenols in water.

A review of recent developments in the speciation and location of arsenic and selenium in rice grain

PubMed Central

Carey, Anne-Marie; Lombi, Enzo; Donner, Erica; de Jonge, Martin D.; Punshon, Tracy; Jackson, Brian P.; Guerinot, Mary Lou; Price, Adam H.; Meharg, Andrew A.

2014-01-01

Rice is a staple food yet is a significant dietary source of inorganic arsenic, a class 1, nonthreshold carcinogen. Establishing the location and speciation of arsenic within the edible rice grain is essential for understanding the risk and for developing effective strategies to reduce grain arsenic concentrations. Conversely, selenium is an essential micronutrient and up to 1 billion people worldwide are selenium-deficient. Several studies have suggested that selenium supplementation can reduce the risk of some cancers, generating substantial interest in biofortifying rice. Knowledge of selenium location and speciation is important, because the anti-cancer effects of selenium depend on its speciation. Germanic acid is an arsenite/silicic acid analogue, and location of germanium may help elucidate the mechanisms of arsenite transport into grain. This review summarises recent discoveries in the location and speciation of arsenic, germanium, and selenium in rice grain using state-of-the-art mass spectrometry and synchrotron techniques, and illustrates both the importance of high-sensitivity and high-resolution techniques and the advantages of combining techniques in an integrated quantitative and spatial approach. PMID:22159463

Reduced As Components in Highly Oxidized Environments: Evidence from Full Spectral XANES Imaging using the Maia Massively Parallel Detector

DOE Office of Scientific and Technical Information (OSTI.GOV)

Etschmann, B.; Ryan, C; Brugger, J

2010-01-01

Synchrotron X-ray fluorescence (SXRF) and X-ray absorption spectroscopy (XAS) have become standard tools to measure element concentration, distribution at micrometer- to nanometer-scale, and speciation (e.g., nature of host phase; oxidation state) in inhomogeneous geomaterials. The new Maia X-ray detector system provides a quantum leap for the method in terms of data acquisition rate. It is now possible to rapidly collect fully quantitative maps of the distribution of major and trace elements at micrometer spatial resolution over areas as large as 1 x 5 cm{sup 2}. Fast data acquisition rates also open the way to X-ray absorption near-edge structure (XANES) imaging,more » in which spectroscopic information is available at each pixel in the map. These capabilities are critical for studying inhomogeneous Earth materials. Using a 96-element prototype Maia detector, we imaged thin sections of an oxidized pisolitic regolith (2 x 4.5 mm{sup 2} at 2.5 x 2.5 {micro}m{sup 2} pixel size) and a metamorphosed, sedimentary exhalative Mn-Fe ore (3.3 x 4 mm{sup 2} at 1.25 x 5 {micro}m{sup 2}). In both cases, As K-edge XANES imaging reveals localized occurrence of reduced As in parts of these oxidized samples, which would have been difficult to recognize using traditional approaches.« less

Sulfur speciation and stable isotope trends of water-soluble sulfates in mine tailings profiles.

PubMed

Dold, Bernhard; Spangenberg, Jorge E

2005-08-01

Sulfur speciation and the sources of water-soluble sulfate in three oxidizing sulfidic mine tailings impoundments were investigated by selective dissolution and stable isotopes. The studied tailings impoundments--Piuquenes, Cauquenes, and Salvador No. 1--formed from the exploitation of the Rio Blanco/La Andina, El Teniente, and El Salvador Chilean porphyry copper deposits, which are located in Alpine, Mediterranean, and hyperarid climates, respectively. The water-soluble sulfate may originate from dissolution of primary ore sulfates (e.g., gypsum, anhydrite, jarosite) or from oxidation of sulfide minerals exposed to aerobic conditions during mining activity. With increasing aridity and decreasing pyrite content of the tailings, the sulfur speciation in the unsaturated oxidation zones showed a trend from dominantly Fe(III) oxyhydroxide fixed sulfate (e.g., jarosite and schwertmannite) in Piuquenes toward increasing presence of water-soluble sulfate at Cauquenes and Salvador No. 1. In the saturated primary zones, sulfate is predominantly present in water-soluble form (mainly as anhydrite and/or gypsum). In the unsaturated zone at Piuquenes and Cauquenes, the delta34S(SO4)values ranged from +0.5 per thousand to +2.0 per thousand and from -0.4 per thousand to +1.4 per thousand Vienna Canyon Diablo Troilite (V-CDT), respectively, indicating a major sulfate source from pyrite oxidation (delta34S(pyrite) = -1.1 per thousand and -0.9 per thousand). In the saturated zone at Piuquenes and Cauquenes, the values ranged from -0.8 per thousand to +0.3 per thousand and from +2.2 per thousand to +3.9 per thousand, respectively. At Cauquenes the 34S enrichment in the saturated zone toward depth indicates the increasing contribution of isotopically heavy dissolved sulfate from primary anhydrite (approximately +10.9 per thousand). At El Salvador No. 1, the delta34S(SO4) average value is -0.9 per thousand, suggesting dissolution of supergene sulfate minerals (jarosite, alunite, gypsum) with a delta34S approximately -0.7 per thousand as the most probable sulfate source. The gradual decrease of delta18O(SO4) values from the surface to the oxidation front in the tailings impoundments at Piuquenes (from -4.5 per thousand to -8.6 per thousand Vienna Standard Mean Ocean Water, V-SMOW) and at Cauquenes (from -1.3 per thousand to -3.5 per thousand) indicates the increasing importance of ferric iron as the main electron acceptor in the oxidation of pyrite. The different delta18O(SO4) values between the tailings impoundments studied here reflect the local climates.

Thermal state, oxygen fugacity and COH fluid speciation in cratonic lithospheric mantle: New data on peridotite xenoliths from the Udachnaya kimberlite, Siberia

NASA Astrophysics Data System (ADS)

Goncharov, A. G.; Ionov, D. A.; Doucet, L. S.; Pokhilenko, L. N.

2012-12-01

Oxygen fugacity (fO2) and temperature variations in a complete lithospheric mantle section (70-220 km) of the central Siberian craton are estimated based on 42 peridotite xenoliths in the Udachnaya kimberlite. Pressure and temperature (P-T) estimates for the 70-140 km depth range closely follow the 40 mW/m2 model conductive geotherm but show a bimodal distribution at greater depths. A subset of coarse garnet peridotites at 145-180 km plots near the "cold" 35 mW/m2 geotherm whereas the majority of coarse and sheared rocks at ≥145 km scatter between the 40 and 45 mW/m2 geotherms. This P-T profile may reflect a perturbation of an initially "cold" lithospheric mantle through a combination of (1) magmatic under-plating close to the crust-mantle boundary and (2) intrusion of melts/fluids in the lower lithosphere accompanied by shearing. fO2 values estimated from Fe3+/∑Fe in spinel and/or garnet obtained by Mössbauer spectroscopy decrease from +1 to -4 Δlog fO2 (FMQ) from the top to the bottom of the lithospheric mantle (˜0.25 log units per 10 km) due to pressure effects on Fe2+-Fe3+ equilibria in garnet. Garnet peridotites from Udachnaya appear to be more oxidized than those from the Kaapvaal craton but show fO2 distribution with depth similar to those in the Slave craton. Published fO2 estimates for Udachnaya xenoliths based on C-O-H fluid speciation in inclusions in minerals from gas chromatography are similar to our results at ≤120 km, but are 1-2 orders of magnitude higher for the deeper mantle, possibly due to uncertainties of fO2 estimates based on experimental calibrations at ≤3.5 GPa. Sheared peridotites containing garnets with u-shaped, sinusoidal and humped REE patterns are usually more oxidized than Yb, Lu-rich, melt-equilibrated garnets, which show a continuous decrease from heavy to light REE. This further indicates that mantle redox state may be related to sources and modes of metasomatism.

Arsenic microdistribution and speciation in toenail clippings of children living in a historic gold mining area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearce, Dora C.; Dowling, Kim; Gerson, Andrea R.

2010-05-04

Arsenic is naturally associated with gold mineralization and elevated in some soils and mine waste around historical gold mining activity in Victoria, Australia. To explore uptake, arsenic concentrations in children's toenail clippings and household soils were measured, and the microdistribution and speciation of arsenic in situ in toenail clipping thin sections investigated using synchrotron-based X-ray microprobe techniques. The ability to differentiate exogenous arsenic was explored by investigating surface contamination on cleaned clippings using depth profiling, and direct diffusion of arsenic into incubated clippings. Total arsenic concentrations ranged from 0.15 to 2.1 {micro}g/g (n = 29) in clipping samples and frommore » 3.3 to 130 {micro}g/g (n = 22) in household soils, with significant correlation between transformed arsenic concentrations (Pearson's r = 0.42, P = 0.023) when household soil was treated as independent. In clipping thin sections (n = 2), X-ray fluorescence (XRF) mapping showed discrete layering of arsenic consistent with nail structure, and irregular arsenic incorporation along the nail growth axis. Arsenic concentrations were heterogeneous at 10 x 10 {micro}m microprobe spot locations investigated (< 0.1 to 13.3 {micro}g/g). X-ray absorption near-edge structure (XANES) spectra suggested the presence of two distinct arsenic species: a lower oxidation state species, possibly with mixed sulphur and methyl coordination (denoted As{sub (-S, -ch3)}{sup {approx}III}); and a higher oxidation state species (denoted As{sub (-O)}{sup {approx}V}). Depth profiling suggested that surface contamination was unlikely (n = 4), and XRF and XANES analyses of thin sections of clippings incubated in dry or wet mine waste, or untreated, suggested direct diffusion of arsenic occurred under moist conditions. These findings suggest that arsenic in soil contributes to some systemic absorption associated with periodic exposures among children resident in areas of historic gold mining activity in Victoria, Australia. Future studies are required to ascertain if adverse health effects are associated with current levels of arsenic uptake.« less

Speciation of hexavalent chromium in welding fumes interference by air oxidation of chromium.

PubMed

Zatka, V J

1985-06-01

The determination of various chromium species in welding fume normally involves digestion in a hot alkaline solution. This work confirms that Cr(III) can be oxidized to Cr(VI) during this digestion. However, only dissolved forms of Cr(III), such as the hydroxochromate(III) ion, [Cr(OH)4], are susceptible to oxidation under these conditions. The air oxidation of Cr(III) can be prevented by hydrolytic destabilization of the hydroxochromate(III) complex by the presence of magnesium hydroxide precipitate. The procedure has been used successfully in the determination of insoluble chromium(VI) in welding fumes. Excellent reproducibility is documented for soluble and insoluble chromium(VI) fractions in the analysis of a bulk sample of welding fume.

Assessing element distribution and speciation in a stream at abandoned Pb-Zn mining site by combining classical, in-situ DGT and modelling approaches.

PubMed

Omanović, Dario; Pižeta, Ivanka; Vukosav, Petra; Kovács, Elza; Frančišković-Bilinski, Stanislav; Tamás, János

2015-04-01

The distribution and speciation of elements along a stream subjected to neutralised acid mine drainage (NAMD) effluent waters (Mátra Mountain, Hungary; Toka stream) were studied by a multi-methodological approach: dissolved and particulate fractions of elements were determined by HR-ICPMS, whereas speciation was carried out by DGT, supported by speciation modelling performed by Visual MINTEQ. Before the NAMD discharge, the Toka is considered as a pristine stream, with averages of dissolved concentrations of elements lower than world averages. A considerable increase of element concentrations caused by effluent water inflow is followed by a sharp or gradual concentration decrease. A large difference between total and dissolved concentrations was found for Fe, Al, Pb, Cu, Zn and As in effluent water and at the first downstream site, with high correlation factors between elements in particulate fraction, indicating their common behaviour, governed by the formation of ferri(hydr)oxides (co)precipitates. In-situ speciation by the DGT technique revealed that Zn, Cd, Ni, Co, Mn and U were predominantly present as a labile, potentially bioavailable fraction (>90%). The formation of strong complexes with dissolved organic matter (DOM) resulted in a relatively low DGT-labile concentration of Cu (42%), while low DGT-labile concentrations of Fe (5%) and Pb (12%) were presumably caused by their existence in colloidal (particulate) fraction which is not accessible to DGT. Except for Fe and Pb, a very good agreement between DGT-labile concentrations and those predicted by the applied speciation model was obtained, with an average correlation factor of 0.96. This study showed that the in-situ DGT technique in combination with model-predicted speciation and classical analysis of samples could provide a reasonable set of data for the assessment of the water quality status (WQS), as well as for the more general study of overall behaviour of the elements in natural waters subjected to high element loads. Copyright © 2014 Elsevier B.V. All rights reserved.

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

Water-Rock Reactions on Non-Planetary Bodies in the Early Solar System

NASA Astrophysics Data System (ADS)

Zolotov, M. Y.

2005-12-01

Reactions of aqueous fluids with rocks shortly after formation of the solar system affected the oxidation states, mineralogy, organic speciation, ice composition, and surface/atmospheric chemistry of asteroids, icy satellites of giant plants, and possibly Kuiper belt objects. Water condensed as ice in the solar nebula, was incorporated into the composition of these bodies together with rocky components represented by extremely reduced and anhydrous nebular condensates (e.g., Fe-rich metal, forsterite, low-Ca pyroxene, troilite, Ca-Mg-Al oxides, phosphides), presolar grains (SiC, graphite, diamond, Al-, Mg-, Ti-oxides) and organic compounds and polymers. Radioactive decay of short-lived radionuclides on small bodies, and accretionary heat and decay of long-lived radionuclides on large bodies provided energy to melt ice. On smaller bodies, low gravity precluded separation of water from rocks and restricted fluid dynamics. On larger bodies, water was separated from descending rocks, limiting the duration of water-rock reactions. Competitive oxidation and hydration by water affected both inorganic and organic compounds in rocks. Oxidation of minerals led to formation of ferrous silicates, magnetite, pyrrhotite, Ni sulfides, Ni-rich metal alloys, chromite, phosphates, carbonates and sulfates. Hydration caused formation of phyllosilicates (serpentine, chlorites, smectite clays, amphiboles, and micas), hydroxides, and hydrated sulfides and salts. High water/rock ratios, elevated temperatures and low pressures favored oxidation. Low temperatures supported hydration. In some icy satellites (Europa, Ganymede) high water content and hydrothermal processes during differentiation may have caused profound oxidation leading to carbonates and even sulfates. Since water was the only early oxidizing agent, the elevated oxidation state of Io implies its early aqueous history. Hydrogen was produced in all oxidation reactions and preferentially separated into the gas phase. Escape of H2 into space promoted oxidation, consistent with the high oxidation state of highly porous CI and CM carbonaceous chondrites. Low porosity and permeability, filling of pore space with secondary minerals, and sealing of outer zones with ice restricted H2 escape, retarded some oxidation reactions and caused incomplete reduction of minerals formed earlier by oxidation. For example, magnetite was partially converted to ferrous silicates. The limited oxidation and signs of reduction in some meteorite types (unequilibrated ordinary and CV3 carbonaceous chondrites) is consistent with low amounts of incorporated water ice and low porosity of parent asteroids. Although prolonged heating of bodies caused dehydration and some reduction, water-rock reactions led to net oxidation of primary rocky components, consistent with the elevated oxidation states of metamorphosed chondrites and Io. Interaction of water with organic compounds and carbon grains caused disproportionation of carbon leading to O-bearing organic compounds and CO2, as well as to hydrogenated organic compounds and methane. In small bodies, organic matter was only partially altered. In some icy satellites, prolonged reactions and elevated pressures favored formation of light hydrocarbons and methane, consistent with observations (e.g., Titan, Triton). In most bodies, net oxidation of organic compounds can be attributed to preservation of CO2 and O-bearing organics in solution, ices and carbonates, and escape of H2 formed through oxidation reactions.

Multi-scale analysis of the occurrence of Pb, Cr and Mn in the NIST standards: Urban dust (SRM 1649a) and indoor dust (SRM 2584)

NASA Astrophysics Data System (ADS)

Jiang, Mingyu; Nakamatsu, Yuki; Jensen, Keld A.; Utsunomiya, Satoshi

2014-01-01

Adverse health effects of ambient particulate matters are closely related to the speciation of the constituting organic matters and toxic metals. To determine multi-parameters of the metal speciation in urban and indoor dusts, we have performed systematic bulk- to nano-scale (“multi-scale”) analysis on the speciation of Pb, Mn, and Cr in two National Institute of Standards and Technology (NIST) standard reference materials (SRMs): urban dust (SRM 1649a) and indoor dust (SRM 2584), utilizing X-ray absorption near-edge structure, powder X-ray diffraction analysis, electron microprobe analysis, scanning electron microscopy, and transmission electron microscopy. Major crystalline phases are quartz, gypsum, kaolinite, and muscovite in SRM 1649a, while quartz, gypsum, calcite, and possibly muscovite (or chabazite) in SRM 2584. A number of Pb sulfate nanoparticles (50-200 nm) occur in SRM 1649a, whereas micron-sized Pb carbonate is present containing various concentrations of Zn and Ti in the complex texture in SRM 2584. Relatively soluble Mn(II) sulfate is the bulk-averaged Mn speciation in SRM 1649a, although discrete Mn sulfate particles are not characterized by individual particle analysis, implying the diluted Mn distribution within other sulfate. In SRM 2584, Mn speciation includes a mixture of oxides and carbonates, and trace Mn in chromite. Chromite (FeCr2O4) is the major Cr speciation in SRM1694a, while unidentified Cr(III) phases with minor chromite and Pb chromate are present in SRM 2584, among which the Pb chromate is composed of Cr(VI). A significant number of the metal-bearing particles are distributed to the submicron-size fraction in the urban dust, SRM 1649a, suggesting that these metal nanoparticles can potentially penetrate into the deep respiratory system. This study demonstrates that multi-scale analysis combining nano and bulk analytical techniques is a powerful approach to investigate the multi-parameters of metal-bearing nanoparticles in heterogeneous PM samples.

X-ray absorption spectroscopy and imaging of heterogeneous hydrothermal mixtures using a diamond microreactor cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulton, John L.; Darab, John G.; Hoffmann, Markus M.

2001-04-01

Hydrothermal synthesis is an important route to novel materials. Hydrothermal chemistry is also an important aspect of geochemistry and a variety of waste remediation technologies. There is a significant lack of information about the speciation of inorganic compounds under hydrothermal conditions. For these reasons we describe a high-temperature, high-pressure cell that allows one to acquire both x-ray absorption fine structure (XAFS) spectra and x-ray transmission and absorption images of heterogeneous hydrothermal mixtures. We demonstrate the utility of the method by measuring the Cu(I) speciation in a solution containing both solid and dissolved Cu phases at temperatures up to 325{sup o}C.more » X-ray imaging of the various hydrothermal phases allows micro-XAFS to be collected from different phases within the heterogeneous mixture. The complete structural characterization of a soluble bichloro-cuprous species was determined. In situ XAFS measurements were used to define the oxidation state and the first-shell coordination structure. The Cu--Cl distance was determined to be 2.12 Aa for the CuCl{sub 2}{sup -} species and the complete loss of tightly bound waters of hydration in the first shell was observed. The microreactor cell described here can be used to test thermodynamic models of solubility and redox chemistry of a variety of different hydrothermal mixtures.« less

Identification of the typical metal particles among haze, fog, and clear episodes in the Beijing atmosphere.

PubMed

Hu, Yunjie; Lin, Jun; Zhang, Suanqin; Kong, Lingdong; Fu, Hongbo; Chen, Jianmin

2015-04-01

For a better understanding of metal particle morphology and behaviors in China, atmospheric aerosols were sampled in the summer of 2012 in Beijing. The single-particle analysis shows various metal-bearing speciations, dominated by oxides, sulfates and nitrates. A large fraction of particles is soluble. Sources of Fe-bearing particles are mainly steel industries and oil fuel combustion, whereas Zn- and Pb-bearing particles are primarily contributed by waste incineration, besides industrial combustion. Other trace metal particles play a minor rule, and may come from diverse origins. Mineral dust and anthropogenic source like vehicles and construction activities are of less importance to metal-rich particles. Statistics of 1173 analyzed particles show that Fe-rich particles (48.5%) dominate the metal particles, followed by Zn-rich particles (34.9%) and Pb-rich particles (15.6%). Compared with the abundances among clear, haze and fog conditions, a severe metal pollution is identified in haze and fog episodes. Particle composition and elemental correlation suggest that the haze episodes are affected by the biomass burning in the southern regions, and the fog episodes by the local emission with manifold particle speciation. Our results show the heterogeneous reaction accelerated in the fog and haze episodes indicated by more zinc nitrate or zinc sulfate instead of zinc oxide or carbonate. Such information is useful in improving our knowledge of fine airborne metal particles on their morphology, speciation, and solubility, all of which will help the government introduce certain control to alleviate metal pollution. Copyright © 2014 Elsevier B.V. All rights reserved.

Lead speciation in indoor dust: a case study to assess old paint contribution in a Canadian urban house

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beauchemin, Suzanne; MacLean, Lachlan C.W.; Rasmussen, Pat E.

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg{sup -1}) and dust (200-1,000 mg Pb kg{sup -1}) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pbmore » species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 {micro}m house dust samples. In the dust fraction <36 {micro}m, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.« less

Lead Speciation in Indoor Dust: A Case Study to Assess Old Paint Contribution in a Canadian Urban House

DOE Office of Scientific and Technical Information (OSTI.GOV)

S Beauchemin; L MacLean; P Rasmussen

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg{sup -1}) and dust (200-1,000 mg Pb kg{sup -1}) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pbmore » species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 m house dust samples. In the dust fraction <36 {mu}m, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.« less

Oxidative dissolution potential of biogenic and abiogenic TcO 2 in subsurface sediments

NASA Astrophysics Data System (ADS)

Fredrickson, James K.; Zachara, John M.; Plymale, Andrew E.; Heald, Steve M.; McKinley, James P.; Kennedy, David W.; Liu, Chongxuan; Nachimuthu, Ponnusamy

2009-04-01

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O4-] and less mobile in the reduced form [Tc(IV)O 2· nH 2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO 2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O 2 into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.

Diversification dynamics of rhynchostomatian ciliates: the impact of seven intrinsic traits on speciation and extinction in a microbial group.

PubMed

Vďačný, Peter; Rajter, Ľubomír; Shazib, Shahed Uddin Ahmed; Jang, Seok Won; Shin, Mann Kyoon

2017-08-30

Ciliates are a suitable microbial model to investigate trait-dependent diversification because of their comparatively complex morphology and high diversity. We examined the impact of seven intrinsic traits on speciation, extinction, and net-diversification of rhynchostomatians, a group of comparatively large, predatory ciliates with proboscis carrying a dorsal brush (sensoric structure) and toxicysts (organelles used to kill the prey). Bayesian estimates under the binary-state speciation and extinction model indicate that two types of extrusomes and two-rowed dorsal brush raise diversification through decreasing extinction. On the other hand, the higher number of contractile vacuoles and their dorsal location likely increase diversification via elevating speciation rate. Particular nuclear characteristics, however, do not significantly differ in their diversification rates and hence lineages with various macronuclear patterns and number of micronuclei have similar probabilities to generate new species. Likelihood-based quantitative state diversification analyses suggest that rhynchostomatians conform to Cope's rule in that their diversity linearly grows with increasing body length and relative length of the proboscis. Comparison with other litostomatean ciliates indicates that rhynchostomatians are not among the cladogenically most successful lineages and their survival over several hundred million years could be associated with their comparatively large and complex bodies that reduce the risk of extinction.

Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

NASA Astrophysics Data System (ADS)

Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

2009-12-01

The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration of plutonium in the subsurface.

Assessing when chromosomal rearrangements affect the dynamics of speciation: implications from computer simulations

PubMed Central

Feder, Jeffrey L.; Nosil, Patrik; Flaxman, Samuel M.

2014-01-01

Many hypotheses have been put forth to explain the origin and spread of inversions, and their significance for speciation. Several recent genic models have proposed that inversions promote speciation with gene flow due to the adaptive significance of the genes contained within them and because of the effects inversions have on suppressing recombination. However, the consequences of inversions for the dynamics of genome wide divergence across the speciation continuum remain unclear, an issue we examine here. We review a framework for the genomics of speciation involving the congealing of the genome into alternate adaptive states representing species (“genome wide congealing”). We then place inversions in this context as examples of how genetic hitchhiking can potentially hasten genome wide congealing. Specifically, we use simulation models to (i) examine the conditions under which inversions may speed genome congealing and (ii) quantify predicted magnitudes of these effects. Effects of inversions on promoting speciation were most common and pronounced when inversions were initially fixed between populations before secondary contact and adaptation involved many genes with small fitness effects. Further work is required on the role of underdominance and epistasis between a few loci of major effect within inversions. The results highlight five important aspects of the roles of inversions in speciation: (i) the geographic context of the origins and spread of inversions, (ii) the conditions under which inversions can facilitate divergence, (iii) the magnitude of that facilitation, (iv) the extent to which the buildup of divergence is likely to be biased within vs. outside of inversions, and (v) the dynamics of the appearance and disappearance of exceptional divergence within inversions. We conclude by discussing the empirical challenges in showing that inversions play a central role in facilitating speciation with gene flow. PMID:25206365

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils.

PubMed

LeMonte, Joshua J; Stuckey, Jason W; Sanchez, Joshua Z; Tappero, Ryan; Rinklebe, Jörg; Sparks, Donald L

2017-06-06

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions. We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils

DOE PAGES

LeMonte, Joshua J.; Stuckey, Jason W.; Sanchez, Joshua Z.; ...

2017-05-04

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions.more » We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Here, our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.« less

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

LeMonte, Joshua J.; Stuckey, Jason W.; Sanchez, Joshua Z.

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions.more » We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Here, our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.« less

Chemical forms of sulfur in geological and archeological asphaltenes from Middle East, France, and Spain determined by sulfur K- and L-edge X-ray absorption near-edge structure spectroscopy

NASA Astrophysics Data System (ADS)

Sarret, Géraldine; Connan, Jacques; Kasrai, Masoud; Bancroft, G. Michael; Charrié-Duhaut, Armelle; Lemoine, Sylvie; Adam, Pierre; Albrecht, Pierre; Eybert-Bérard, Laurent

1999-11-01

Asphaltene samples extracted from archeological and geological bitumens from the Middle East, France, and Spain were studied by sulfur K- and L-edge X-ray absorption near-edge structure (XANES) spectroscopy in combination with isotopic analyses (δ 13C and δD). Within each series, the samples were genetically related by their δ 13C values. The gross and elemental composition and the δD values were used to characterize the weathering state of the samples. Sulfur K- and L-edge XANES results show that in all the samples, dibenzothiophenes are the dominant forms of sulfur. In the least oxidized asphaltenes, minor species include disulfides, alkyl and aryl sulfides, and sulfoxides. With increasing alteration the proportion of oxidized sulfur (sulfoxides, sulfones, sulfonates and sulfates) increases, whereas the disulfide and sulfide content decreases. This evolution is observed in all the series, regardless of the origin of the asphaltenes. This work illustrates the advantages of XANES spectroscopy as a selective probe for determining sulfur speciation in natural samples. It also shows that S K- and L-edge XANES spectroscopy are complementary for identifying the oxidized and reduced forms of sulfur, respectively.

Impact of phenazine-1-carboxylic acid upon iron speciation and microbial biomass in the rhizosphere of wheat

NASA Astrophysics Data System (ADS)

LeTourneau, M.; Marshall, M.; Grant, M.; Freeze, P.; Cliff, J. B.; Lai, B.; Strawn, D. G.; Thomashow, L. S.; Weller, D. M.; Harsh, J. B.

2015-12-01

Phenazine-1-carboxylic acid (PCA) is a redox-active antibiotic produced by diverse bacterial taxa, and has been shown to facilitate interactions between biofilms and iron (hydr)oxides in culture systems (Wang et al. 2011, J Bacteriol 192: 365). Because rhizobacterial biofilms are a major sink for plant-derived carbon and source for soil organic matter (SOM), and Fe (hydr)oxides have reactive surfaces that influence the stability of microbial biomass and SOM, PCA-producing rhizobacteria could influence soil carbon fluxes. Large populations of Pseudomonas fluorescens strains producing PCA in concentrations up to 1 μg/g root have been observed in the rhizosphere of non-irrigated wheat fields covering 1.56 million hectares of central Washington state. This is one of the highest concentrations ever reported for a natural antibiotic in a terrestrial ecosystem (Mavrodi et al. 2012, Appl Environ Microb 78: 804). Microscopic comparisons of PCA-producing (PCA+) and non-PCA-producing (PCA-) rhizobacterial colony morphologies, and comparisons of Fe extractions from rhizosphere soil inoculated with PCA+ and PCA- strains suggest that PCA promotes biofilm development as well as dramatic Fe transformations throughout the rhizosphere (unpublished data). In order to illustrate PCA-mediated interactions between biofilms and Fe (hydr)oxides in the rhizosphere, identify the specific Fe phases favored by PCA, and establish the ramifications for stability and distribution of microbial biomass and SOM, we have collected electron micrographs, X-ray fluorescence images, X-ray absorption near-edge spectra, and secondary-ion mass spectrometry images of wheat root sections inoculated with 15N-labelled PCA+ or PCA- rhizobacteria. These images and spectra allow us to assess the accumulation, turnover, and distribution of microbial biomass, the associations between Fe and other nutrients such as phosphorus, and the redox status and speciation of iron in the presence and absence of PCA. This information provides a starting point to model the impact of PCA upon carbon fluxes in Columbia Basin agro-ecosystems and other environments where PCA-producing bacteria are prevalent.

Fingerprinting the reactive toxicity pathways of 50 drinking water disinfection by-products.

PubMed

Stalter, Daniel; O'Malley, Elissa; von Gunten, Urs; Escher, Beate I

2016-03-15

A set of nine in vitro cellular bioassays indicative of different stages of the cellular toxicity pathway was applied to 50 disinfection by-products (DBPs) to obtain a better understanding of the commonalities and differences in the molecular mechanisms of reactive toxicity of DBPs. An Eschericia coli test battery revealed reactivity towards proteins/peptides for 64% of the compounds. 98% activated the NRf2-mediated oxidative stress response and 68% induced an adaptive stress response to genotoxic effects as indicated by the activation of the tumor suppressor protein p53. All DBPs reactive towards DNA in the E. coli assay and activating p53 also induced oxidative stress, confirming earlier studies that the latter could trigger DBP's carcinogenicity. The energy of the lowest unoccupied molecular orbital ELUMO as reactivity descriptor was linearly correlated with oxidative stress induction for trihalomethanes (r(2)=0.98) and haloacetamides (r(2)=0.58), indicating that potency of these DBPs is connected to electrophilicity. However, the descriptive power was poor for haloacetic acids (HAAs) and haloacetonitriles (r(2) (<) 0.06). For HAAs, we additionally accounted for speciation by including the acidity constant with ELUMO in a two-parameter multiple linear regression model. This increased r(2) to >0.80, indicating that HAAs' potency is connected to both, electrophilicity and speciation. Based on the activation of oxidative stress response and the soft electrophilic character of most tested DBPs we hypothesize that indirect genotoxicity-e.g., through oxidative stress induction and/or enzyme inhibition-is more plausible than direct DNA damage for most investigated DBPs. The results provide not only a mechanistic understanding of the cellular effects of DBPs but the effect concentrations may also serve to evaluate mixture effects of DBPs in water samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Arsenite and ferrous iron oxidation linked to chemolithotrophic denitrification for the immobilization of arsenic in anoxic environments

USGS Publications Warehouse

Sun, W.; Sierra-Alvarez, R.; Milner, L.; Oremland, R.; Field, J.A.

2009-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3- to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flows and filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (column SF1) or absence (column SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 ??g L-1 was reduced to 10.6 (??9.6) ??g L-1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5 to 10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns were close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxide coated sands with adsorbed As(V). ?? 2009 American Chemical Society.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tribble, G.W.

A combination of field and theoretical work is used to study controls on the saturation state of aragonite inside a coral-reef framework. A closed-system ion-speciation model is used to evaluate the effect of organic-matter oxidation on the saturation state of aragonite. The aragonite saturation state initially drops below 1 but becomes oversaturated during sulfate reduction. The C:N ratio of the organic matter affects the degree of oversaturation with N-poor organic material resulting in a system more corrosive to aragonite. Precipitation of sulfide as FeS strongly affects the aragonite saturation state, and systems with much FeS formation will have a strongermore » tendency to become oversaturated with respect to aragonite. Both precipitation and dissolution of aragonite are predicted at different stages of the organic reaction pathway if the model system is maintained at aragonite saturation. Field data from a coral-reef framework indicate that the system maintains itself at aragonite saturation, and model-predicted changes in dissolved calcium follow those observed in the interstitial waters of the reef. Aragonite probably acts as a solid-phase buffer in regulating the pH of interstitial waters. Because interstitial water in the reef has a short residence time, the observed equilibration suggests rapid kinetics.« less

Local vs Nonlocal States in FeTiO3 Probed with 1s2pRIXS: Implications for Photochemistry

PubMed Central

2017-01-01

Metal–metal charge transfer (MMCT) is expected to be the main mechanism that enables the harvesting of solar light by iron–titanium oxides for photocatalysis. We have studied FeTiO3 as a model compound for MMCT with 1s2pRIXS at the Fe K-edge. The high-energy resolution XANES enables distinguishing five pre-edge features. The three first well distinct RIXS features are assigned to electric quadrupole transitions to the localized Fe* 3d states, shifted to lower energy by the 1s core–hole. Crystal field multiplet calculations confirm the speciation of divalent iron. The contribution of electric dipole absorption due to local p-d mixing allowed by the trigonal distortion of the cation site is supported by DFT and CFM calculations. The two other nonlocal features are assigned to electric dipole transitions to excited Fe* 4p states mixed with the neighboring Ti 3d states. The comparison with DFT calculations demonstrates that MMCT in ilmenite is favored by the hybridization between the Fe 4p and delocalized Ti 3d orbitals via the O 2p orbitals. PMID:28872322

Local vs Nonlocal States in FeTiO3 Probed with 1s2pRIXS: Implications for Photochemistry.

PubMed

Hunault, Myrtille O J Y; Khan, Wilayat; Minár, Jan; Kroll, Thomas; Sokaras, Dimosthenis; Zimmermann, Patric; Delgado-Jaime, Mario U; de Groot, Frank M F

2017-09-18

Metal-metal charge transfer (MMCT) is expected to be the main mechanism that enables the harvesting of solar light by iron-titanium oxides for photocatalysis. We have studied FeTiO 3 as a model compound for MMCT with 1s2pRIXS at the Fe K-edge. The high-energy resolution XANES enables distinguishing five pre-edge features. The three first well distinct RIXS features are assigned to electric quadrupole transitions to the localized Fe* 3d states, shifted to lower energy by the 1s core-hole. Crystal field multiplet calculations confirm the speciation of divalent iron. The contribution of electric dipole absorption due to local p-d mixing allowed by the trigonal distortion of the cation site is supported by DFT and CFM calculations. The two other nonlocal features are assigned to electric dipole transitions to excited Fe* 4p states mixed with the neighboring Ti 3d states. The comparison with DFT calculations demonstrates that MMCT in ilmenite is favored by the hybridization between the Fe 4p and delocalized Ti 3d orbitals via the O 2p orbitals.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

An XPS study on the impact of relative humidity on the aging of UO 2 powders

DOE PAGES

Donald, Scott B.; Dai, Zurong R.; Davisson, M. Lee; ...

2017-02-10

High resolution x-ray photoemission spectroscopy (XPS) was used to characterize the chemical speciation of high purity uranium dioxide (UO 2) powder samples following aging for periods of up to one year under controlled conditions with relative humidity ranging from 34% to 98%. A systematic shift to higher uranium oxidation states, and thus an increase in the mean uranium valence, was found to directly correlate with the dose of water received (i.e. the product of exposure time and relative humidity). Exposure duration was found to have a greater impact on sample aging than relative humidity. Lastly, the sample aged at 98%more » relative humidity was found to have unique structural differences for exposure time beyond 180 days when observed by scanning electron microscopy (SEM).« less

An XPS study on the impact of relative humidity on the aging of UO 2 powders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donald, Scott B.; Dai, Zurong R.; Davisson, M. Lee

High resolution x-ray photoemission spectroscopy (XPS) was used to characterize the chemical speciation of high purity uranium dioxide (UO 2) powder samples following aging for periods of up to one year under controlled conditions with relative humidity ranging from 34% to 98%. A systematic shift to higher uranium oxidation states, and thus an increase in the mean uranium valence, was found to directly correlate with the dose of water received (i.e. the product of exposure time and relative humidity). Exposure duration was found to have a greater impact on sample aging than relative humidity. Lastly, the sample aged at 98%more » relative humidity was found to have unique structural differences for exposure time beyond 180 days when observed by scanning electron microscopy (SEM).« less

The role of arbuscular mycorrhiza on change of heavy metal speciation in rhizosphere of maize in wastewater irrigated agriculture soil.

PubMed

Huang, Yi; Tao, Shu; Chen, You-jian

2005-01-01

To understand the roles of mycorrhiza in metal speciation in the rhizosphere and the impact on increasing host plant tolerance against excessive heavy metals in soil, maize (Zea mays L.) inoculated with arbuscular mycorrhizal fungus (Glomus mosseae) was cultivated in heavy metal contaminated soil. Speciations of copper, zinc and lead in the soil were analyzed with the technique of sequential extraction. The results showed that, in comparison to the bolked soil, the exchangeable copper increased from 26% to 43% in non-infected and AM-infected rhizoshpere respectively; while other speciation (organic, carbonate and Fe-Mn oxide copper) remained constant and the organic bound zinc and lead also increased but the exchangeable zinc and lead were undetectable. The organic bound copper, zinc and lead were higher by 15%, 40% and 20%, respectively, in the rhizosphere of arbuscular mycorrhiza infected maize in comparison to the non-infected maize. The results might indicate that mycorrhiza could protect its host plants from the phytotoxicity of excessive copper, zinc and lead by changing the speciation from bio-available to the non-bio-available form. The fact that copper and zinc accumulation in the roots and shoots of mycorrhia infected plants were significantly lower than those in the non-infected plants might also suggest that mycorrhiza efficiently restricted excessive copper and zinc absorptions into the host plants. Compared to the non-infected seedlings, the lead content of infected seedlings was 60% higher in shoots. This might illustrate that mycorrhiza have a different mechanism for protecting its host from excessive lead phytotoxicity by chelating lead in the shoots.

Environmental and health impacts of fine and ultrafine metallic particles: assessment of threat scores.

PubMed

Goix, Sylvaine; Lévêque, Thibaut; Xiong, Tian-Tian; Schreck, Eva; Baeza-Squiban, Armelle; Geret, Florence; Uzu, Gaëlle; Austruy, Annabelle; Dumat, Camille

2014-08-01

This study proposes global threat scores to prioritize the harmfulness of anthropogenic fine and ultrafine metallic particles (FMP) emitted into the atmosphere at the global scale. (Eco)toxicity of physicochemically characterized FMP oxides for metals currently observed in the atmosphere (CdO, CuO, PbO, PbSO(4), Sb(2)O(3), and ZnO) was assessed by performing complementary in vitro tests: ecotoxicity, human bioaccessibility, cytotoxicity, and oxidative potential. Using an innovative methodology based on the combination of (eco)toxicity and physicochemical results, the following hazard classification of the particles is proposed: CdCl2~CdO>CuO>PbO>ZnO>PbSO(4)>Sb(2)O(3). Both cadmium compounds exhibited the highest threat score due to their high cytotoxicity and bioaccessible dose, whatever their solubility and speciation, suggesting that cadmium toxicity is due to its chemical form rather than its physical form. In contrast, the Sb(2)O(3) threat score was the lowest due to particles with low specific area and solubility, with no effects except a slight oxidative stress. As FMP physicochemical properties reveal differences in specific area, crystallization systems, dissolution process, and speciation, various mechanisms may influence their biological impact. Finally, this newly developed and global approach could be widely used in various contexts of pollution by complex metal particles and may improve risk management. Copyright © 2014 Elsevier Inc. All rights reserved.

Solid surface photochemistry of montmorillonite: mechanisms for the arsenite oxidation under UV-A irradiation.

PubMed

Yuan, Yanan; Wang, Yajie; Ding, Wei; Li, Jinjun; Wu, Feng

2016-01-01

Transformation of inorganic arsenic species has drawn great concern in recent decades because of worldwide and speciation-dependent pollution and the hazards that they pose to the environment and to human health. As(III) photooxidation in aquatic systems has received much attention, but little is known about photochemical transformation of arsenic species on top soil. As(III) photooxidation on natural montmorillonite under UV-A radiation was investigated by using a moisture- and temperature-controlled photochemical chamber with two black-light lamps. Initial As(III) concentration, pH, layer thickness, humic acid (HA) concentration, the presence of additional iron ions, and the contribution of reactive oxygen species (ROS) were examined. The results show that pH values of the clay layers greatly influenced As(III) photooxidation on montmorillonite. As(III) photooxidation followed the Langmuir-Hinshelwood model. HA and additional iron ions greatly promoted photooxidation, but excess Fe(II) competed with As(III) for oxidation by ROS. Scavenging experiments revealed that natural montmorillonite induced the conversion of As(III) to As(V) by generating ROS (mainly HO(•) and HO2(•)/O2(•-)) and that HO(•) radical was the predominant oxidant in this system. Our work demonstrates that photooxidation on the surface of natural clay minerals in top soil can be important to As(III) transformation. This allows understanding and predicting the speciation and behavior of arsenic on the soil surface.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

PubMed

Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine

2016-04-05

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Adding to the Mercury Speciation Toolbox

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Northrup, P. A.; Chidambaram, D.; Kalb, P. D.

2007-12-01

Mercury was used to separate lithium-6 isotope for weapons production at the Y-12 Plant in Oak Ridge, TN in the 1950s and 1960s. A large portion of the waste Hg entered the environment and continues to move throughout the sub-surface and surface waters in the area. Environmental management of Hg contamination within this complex hydrologic system, where Hg speciation and the mobile fraction have been found to vary widely, will require ongoing characterization and predictive modeling of Hg speciation. State-of-the-art spectroscopic tools that can directly probe Hg speciation in preserved aqueous and sediment samples with greater sensitivity, however, are required to determine rates and mechanisms of biogeochemical reactions. We will present the first results demonstrating the use of x-ray absorption spectroscopy (XAS) at the Hg M5 edge (2295 eV) to fingerprint Hg species. Heavy-metal M5 absorption edges can have very sharp features due to local electron transitions, and therefore, we are developing this edge as a tool for quantitative measurement of Hg species. In addition, sulfur speciation using the sulfur K absorption edge, which is at a similar energy (2472 eV), can be measured in the same scan as the Hg M5 edge. Potentially important organic and inorganic sulfur species (sulfide, disulfide, elemental sulfur, sulfite and sulfate) are readily differentiated, and thereby, provides an independent method for monitoring the redox state of the system along with changes in S-Hg bonding. We will also present x-ray microprobe 2-D concentration maps of Hg and other elements at the grain and pore scales to identify its microscopic distribution and chemical associations. When used in combination with established sequential extraction and direct spectroscopic methods, the addition of XAS at the Hg M5 edge should provide a significant advancement in the determination of Hg speciation in complex biogeochemical environments.

Arsenic distribution and valence state variation studied by fast hierarchical length-scale morphological, compositional, and speciation imaging at the Nanoscopium, Synchrotron Soleil

NASA Astrophysics Data System (ADS)

Somogyi, Andrea; Medjoubi, Kadda; Sancho-Tomas, Maria; Visscher, P. T.; Baranton, Gil; Philippot, Pascal

2017-09-01

The understanding of real complex geological, environmental and geo-biological processes depends increasingly on in-depth non-invasive study of chemical composition and morphology. In this paper we used scanning hard X-ray nanoprobe techniques in order to study the elemental composition, morphology and As speciation in complex highly heterogeneous geological samples. Multivariate statistical analytical techniques, such as principal component analysis and clustering were used for data interpretation. These measurements revealed the quantitative and valance state inhomogeneity of As and its relation to the total compositional and morphological variation of the sample at sub-μm scales.

Speciation of adsorbates on surface of solids by infrared spectroscopy and chemometrics.

PubMed

Vilmin, Franck; Bazin, Philippe; Thibault-Starzyk, Frédéric; Travert, Arnaud

2015-09-03

Speciation, i.e. identification and quantification, of surface species on heterogeneous surfaces by infrared spectroscopy is important in many fields but remains a challenging task when facing strongly overlapped spectra of multiple adspecies. Here, we propose a new methodology, combining state of the art instrumental developments for quantitative infrared spectroscopy of adspecies and chemometrics tools, mainly a novel data processing algorithm, called SORB-MCR (SOft modeling by Recursive Based-Multivariate Curve Resolution) and multivariate calibration. After formal transposition of the general linear mixture model to adsorption spectral data, the main issues, i.e. validity of Beer-Lambert law and rank deficiency problems, are theoretically discussed. Then, the methodology is exposed through application to two case studies, each of them characterized by a specific type of rank deficiency: (i) speciation of physisorbed water species over a hydrated silica surface, and (ii) speciation (chemisorption and physisorption) of a silane probe molecule over a dehydrated silica surface. In both cases, we demonstrate the relevance of this approach which leads to a thorough surface speciation based on comprehensive and fully interpretable multivariate quantitative models. Limitations and drawbacks of the methodology are also underlined. Copyright © 2015 Elsevier B.V. All rights reserved.

Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems.

PubMed

Cheng, Hefa; Hu, Yuanan; Luo, Jian; Xu, Bin; Zhao, Jianfu

2009-06-15

Acid mine drainage (AMD) is often accompanied with elevated concentrations of arsenic, in the forms of arsenite, As(III), and/or arsenate, As(V), due to the high affinity of arsenic for sulfide mineral ores. This review summarizes the major geochemical processes controlling the release, speciation, fate, and distribution of inorganic arsenic in mine drainage and natural systems. Arsenic speciation depends highly on redox potential and pH of the solution, and arsenite can be oxidized to the less toxic arsenate form. Homogeneous oxidation of arsenite occurs rather slowly while its heterogeneous oxidation on mineral surfaces can greatly enhance the reaction rates. Little evidence suggests that precipitation reaction limits the concentrations of arsenic in natural water, while co-precipitation may lead to rapid arsenic removal when large amount of iron hydroxides precipitate out of the aqueous phase upon neutralization of the mine drainage. Both arsenate and arsenite adsorb on common metal oxides and clay minerals through formation of inner-sphere and/or outer-sphere complexes, controlling arsenic concentration in natural water bodies. Arsenite adsorbs less strongly than arsenate in the typical pH range of natural water and is more mobile. Part of the adsorbed arsenic species can be exchanged by common anions (e.g., PO(4)(3-) and SO(4)(2-)), especially phosphate, which leads to their re-mobilization. Understanding the geochemistry of arsenic is helpful for predicting its mobility and fate in AMD and natural systems, and for designing of cost-effective remediation/treatment strategies to reduce the occurrence and risk of arsenic contamination.

Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2015-12-01

Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.

Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

NASA Technical Reports Server (NTRS)

Hudman, Rynda C.; Jacob, Daniel J.; Turquety, Solene; Leinbensperger, E. M.; Murray, L. T.; Wu, Samuel; Gilliland, A. B.; Avery, Melody A.; Bertram, Timothy H.; Brune, W. H.;

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy.

PubMed

Sahu, M; Gupta, Santosh K; Jain, D; Saxena, M K; Kadam, R M

2018-04-15

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr 2 CeO 4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr 2 CeO 4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, impedance spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr 2 CeO 4 which has tendency to decompose peritectically to SrCeO 3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr 2 CeO 4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO 6 6- (octahedral uranate) in Sr 2 CeO 4 . Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr 2 CeO 4 and it has two different environments due to its stabilization at both Sr 2+ as well as Ce 4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce 4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr 2 CeO 4 based optoelectronic material as well exploring it for actinides studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Sahu, M.; Gupta, Santosh K.; Jain, D.; Saxena, M. K.; Kadam, R. M.

2018-04-01

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr2CeO4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr2CeO4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, photoluminescence spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr2CeO4 which has tendency to decompose peritectically to SrCeO3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr2CeO4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO66- (octahedral uranate) in Sr2CeO4. Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr2CeO4 and it has two different environments due to its stabilization at both Sr2+ as well as Ce4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr2CeO4 based optoelectronic material as well exploring it for actinides studies.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; arsenic speciation in natural-water samples using laboratory and field methods

USGS Publications Warehouse

Garbarino, John R.; Bednar, Anthony J.; Burkhardt, Mark R.

2002-01-01

Analytical methods for the determination of arsenite [As(III)], arsenate [As(V)], dimethylarsinate (DMA), monomethylarsonate (MMA), and roxarsone in filtered natural-water samples are described. Various analytical methods can be used for the determination, depending on the arsenic species being determined. Arsenic concentration is determined by using inductively coupled plasma-mass spectrometry (ICP-MS) as an arsenic-specific detector for all methods. Laboratory-speciation methods are described that use an ion chromatographic column to separate the arsenic species; the column length, column packing, and mobile phase are dependent on the species of interest. Regardless of the separation technique, the arsenic species are introduced into plasma by eithe rpneumatic nebulization or arsine generation. Analysis times range from 2 to 8 minutes and method detection limits range from 0.1 to 0.6 microgram-arsenic per liter (ug-As/L), 10 to 60 picograms absolute (for a 100-microliter injection), depending on the arsenic species determined and the analytical method used. A field-generation specciation method also is described that uses a strong anion exchange cartridge to separate As(III) from As(V) in the field. As(III) in the eluate and the As(V) in the cartridge extract are determined by direct nebulization ICP-MS. Methylated arsenic species that also are retained on the cartridge will positively bias As(V) results without further laboratory separations. The method detection limit for field speciation is 0.3 ug-As/L. The distribution of arsenic species must be preserved in the field to eliminate changes caused by photochemical oxidation or metal oxyhydroxide precipitation. Preservation techniques, such as refrigeration, the addition of acides, or the additoin of ethylene-diaminetetraacetic acid (EDTA) and the effects of ambient light were tested. Of the preservatives evaluated, EDTA was found to work best with the laboratory- and field-speciation methods for all sample matrices tested. Storing the samples in opaque polytethylene bottles eliminated the effects of photochemical oxidation. The percentage change in As(III):As(V) ratios for an EDTA-preserved acid mine drainage (AMD) sample and ground-water sample during a 3-month period was -5 percent and +3 percent, respectively. The bias and variability of the methods were evaluated by comparing results for total arsenic and As(III), As(V), DMA, and MMA concentrations in ground water, AMD, and surface water. Seventy-one ground-water, 10 AMD, and 24 surface-water samples were analyzed. Concentrations in ground-water samples reached 720 ug-As/L for As(III) and 1080 ug-As/L for As(V); AMD samples reached 12800 ug-As/L for As(III) and 7050 ug-As/L for As(V); and surface-water samples reached 5 ug-As/L for As(III) and As(V). Inorganic arsenic species distribution in the samples ranged from 0 to 90 percent As(III). DMA and MMA were present only in surface-water samples from agricultural areas where the herbicide monosodium methylarsonate was applied; concentrations never exceeded 6 ug-As/L. Statistical analyses indicated that the difference between As(III) and As(V) concentrations for samples preserved with EDTA in opaque bottles and field-speciation results were analytically insignificant at the 95-percent confidence interval. There was no significant difference among the methods tested for total arsenic concentration. Percentage recovery for field samples spiked at 50 ug-As/L and analyzed by the laboratory-speciation method (n=2) ranged from 82 to 100 percent for As(III), 97 to 102 percent for As(V), 90 to 104 percent for DMA, and 81 to 96 percent for MMA; recoveries for samples spiked at 100 ug-As/L and analyzed by the field-speciation method ranged from 102 to 107 percent for As(III) and 105 to 106 percent for As(V). Laboratory-speciation results for Environment Canada reference material SLRS-2 closely matched reported concentrations. Laboratory-speciation metho

First field-based atmospheric observation of the reduction of reactive mercury driven by sunlight

NASA Astrophysics Data System (ADS)

de Foy, Benjamin; Tong, Yindong; Yin, Xiufeng; Zhang, Wei; Kang, Shichang; Zhang, Qianggong; Zhang, Guoshuai; Wang, Xuejun; Schauer, James J.

2016-06-01

Hourly speciated measurements of atmospheric mercury made in a remote, high-altitude site in the Tibetan Plateau revealed the first field observations of the reduction of reactive mercury in the presence of sunlight in the atmosphere. Measurements were collected over four winter months on the shore of Nam Co Lake in the inland Tibetan Plateau. The data was analyzed to identify sources and atmospheric transformations of the speciated mercury compounds. The absence of local anthropogenic sources provided a unique opportunity to examine chemical transformations of mercury. An optimization algorithm was used to determine the parameters of a chemical box model that would match the measured reactive mercury concentrations. This required the presence of a photolytic reduction reaction previously observed in laboratory studies and in power plant plumes. In addition, the model estimated the role of vertical mixing in diluting reactive gaseous mercury during the day, and the role of bromine chemistry in oxidizing gaseous elemental mercury to produce reactive gaseous mercury. This work provides further evidence of the need to add the photolytic reduction reaction of oxidized mercury into atmospheric transport models in order to better simulate mercury deposition.

Mouse arsenic (+3 oxidation state) methyltransferase genotype affects metabolism and tissue dosimetry of arsenicals after arsenite administration in drinking water.

PubMed

Chen, Baowei; Arnold, Lora L; Cohen, Samuel M; Thomas, David J; Le, X Chris

2011-12-01

Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes methylation of inorganic arsenic (iAs) producing a number of methylated arsenic metabolites. Although methylation has been commonly considered a pathway for detoxification of arsenic, some highly reactive methylated arsenicals may contribute to toxicity associated with exposure to inorganic arsenic. Here, adult female wild-type (WT) C57BL/6 mice and female As3mt knockout (KO) mice received drinking water that contained 1, 10, or 25 ppm (mg/l) of arsenite for 33 days and blood, liver, kidney, and lung were taken for arsenic speciation. Genotype markedly affected concentrations of arsenicals in tissues. Summed concentrations of arsenicals in plasma were higher in WT than in KO mice; in red blood cells, summed concentrations of arsenicals were higher in KO than in WT mice. In liver, kidney, and lung, summed concentrations of arsenicals were greater in KO than in WT mice. Although capacity for arsenic methylation is much reduced in KO mice, some mono-, di-, and tri-methylated arsenicals were found in tissues of KO mice, likely reflecting the activity of other tissue methyltransferases or preabsorptive metabolism by the microbiota of the gastrointestinal tract. These results show that the genotype for arsenic methylation determines the phenotypes of arsenic retention and distribution and affects the dose- and organ-dependent toxicity associated with exposure to inorganic arsenic.

Research on chromium and arsenic speciation in atmospheric particulate matter: short review

NASA Astrophysics Data System (ADS)

Nocoń, Katarzyna; Rogula-Kozłowska, Wioletta; Widziewicz, Kamila

2018-01-01

Atmospheric particulate matter (PM) plays an important role in the distribution of elements in the environment. The PM-bound elements penetrates into the other elements of the environment, in two basic forms - those dissolved in the atmospheric precipitation and those permanently bound to PM particles. Those forms differs greatly in their mobility, thus posing a potential threat to living organisms. They can also be an immediate threat, while being inhaled. Chromium (Cr) and arsenic (As) belong to the group of elements whose certain chemical states exhibit toxic properties, that is Cr(VI) and As(III). Thus, recognition of the actual threat posed by Cr and As in the environment, including those present in PM, is possible only through the in depth speciation analysis. Research on the Cr and As speciation in PM, more than the analogous studies of their presence in other compartments of the environment, have been undertaken quite rarely. Hence the knowledge on the speciation of PM-bound As and Cr is still limited. The state of knowledge in the field of PM-bound Cr and As is presented in the paper. The issues related to the characterization and occurrence of Cr and As species in PM, the share of Cr and As species mass in different PM size fractions, and in PM of different origin is also summarized. The analytical techniques used in the speciation analysis of PM-bound Cr and As are also discussed. In the existing literature there is no data on the physical characteristics of Cr and As (bound to a different PM size fractions), and thus it still lack of data needed for a comprehensive assessment of the actual environmental and health threat posed by airborne Cr and As.

Influence of oxygenation on chromium redox reactions with manganese sulfide (MnS(s)).

PubMed

Wadhawan, Amar R; Livi, Kenneth J; Stone, Alan T; Bouwer, Edward J

2015-03-17

Manganese sulfide (MnS(s)) minerals exist in sulfidic environments and can have unique reactive abilities because of sulfide, which is a known reductant, and Mn, the oxyhydroxides of which are known oxidants. This study elucidated the role of MnS(s) in controlling Cr speciation with implications on its fate and toxicity in the natural environment, specifically sulfidic sediments that undergo biogeochemical changes due to sediment resuspension during dredging, bioturbation, and flood events. In continuously mixed batch reaction experiments, aqueous CrVI reduction under anaerobic conditions occurred primarily on the surface of MnS(s) displaying a biphasic behavior- the initial rapid removal of CrVI from solution was followed by a slow decline due to surface passivation by reaction products, mainly sorbed or precipitated CrIII. The reaction progress increased with MnS(s) surface area loading but decreased on increasing CrVI concentration and pH, suggesting that surface site regeneration through product desorption was the rate-controlling mechanism. Below circum-neutral pH, higher solubility of MnS(s) resulted in additional CrVI reduction by reduced sulfur species in solution, whereas increased CrIII solubility lowered surface passivation allowing for more reactive sites to participate in the reaction. Aeration of MnS(s) at pH≥7 caused the formation of a heterogeneous MnIII(hydr)oxide that was composed of hausmanite and manganite. CrVI reoccurrence was observed on aeration of CrVI-spiked MnS(s) from the oxidation of product CrIII. The reoccurrence at pH≥7 was attributed to the oxidation of product CrIII by MnIII(hydr)oxide, whereas the reoccurrence at pH<7 was hypothesized from the oxidation of product CrIII by intermediate aqueous MnIII and/or sulfur species. Just as with Cr, MnS(s) may play an important role in speciation, fate, and transport of other environmental contaminants.

Variability of the health effects of crystalline silica: Fe speciation in industrial quartz reagents and suspended dusts—insights from XAS spectroscopy

NASA Astrophysics Data System (ADS)

Di Benedetto, Francesco; D'Acapito, Francesco; Capacci, Fabio; Fornaciai, Gabriele; Innocenti, Massimo; Montegrossi, Giordano; Oberhauser, Werner; Pardi, Luca A.; Romanelli, Maurizio

2014-03-01

We investigated the speciation of Fe in bulk and in suspended respirable quartz dusts coming from ceramic and iron-casting industrial processes via X-ray absorption spectroscopy, with the aim of contributing to a better understanding of the variability of crystalline silica toxicity. Four different bulk industrial quartz powders, nominally pure quartz samples with Fe contents below 200 ppm, and three respirable dusts filters were selected. Fe speciation was determined in all samples through a coupled study of the X-ray absorption near-edge structure and extended X-ray absorption fine structure regions, operating at the Fe-K edge. Fe speciation revealed common features at the beginning of the different production processes, whereas significant differences were observed on both respirable dusts and bulk dusts exiting from the production process. Namely, a common pollution of the raw quartz dusts by elemental Fe was evidenced and attributed to residuals of the industrial production of quartz materials. Moreover, the respirable samples indicated that reactivity occurs after the suspension of the powders in air. The gravitational selection during the particle suspension consistently allowed us to clearly discriminate between suspended and bulk dusts. On the basis of the obtained results, we provide an apparent spectroscopic discrimination between the raw materials used in the considered industrial processes, and those that are effectively inhaled by workers. In particular, an amorphous FeIII oxide, with an unsaturated coordination sphere, can be related to silica reactivity (and health consequences).

Metal speciation in salt marsh sediments: Influence of halophyte vegetation in salt marshes with different morphology

NASA Astrophysics Data System (ADS)

Pedro, Sílvia; Duarte, Bernardo; Raposo de Almeida, Pedro; Caçador, Isabel

2015-12-01

Salt marshes provide environmental conditions that are known to affect metal speciation in sediments. The elevational gradient along the marsh and consequent differential flooding are some of the major factors influencing halophytic species distribution and coverage due to their differential tolerance to salinity and submersion. Different species, in turn, also have distinct influences on the sediment's metal speciation, and its metal accumulation abilities. The present work aimed to evaluate how different halophyte species in two different salt marshes could influence metal partitioning in the sediment at root depth and how that could differ from bare sediments. Metal speciation in sediments around the roots (rhizosediments) of Halimione portulacoides, Sarcocornia fruticosa and Spartina maritima was determined by sequentially extracting operationally defined fractions with solutions of increasing strength and acidity. Rosário salt marsh generally showed higher concentrations of all metals in the rhizosediments. Metal partitioning was primarily related to the type of metal, with the elements' chemistry overriding the environment's influence on fractionation schemes. The most mobile elements were Cd and Zn, with greater availability being found in non-vegetated sediments. Immobilization in rhizosediments was predominantly influenced by the presence of Fe and Mn oxides, as well as organic complexes. In the more mature of both salt marshes, the differences between vegetated and non-vegetated sediments were more evident regarding S. fruticosa, while in the younger system all halophytes presented significantly different metal partitioning when compared to that of mudflats.

Monoterpene chemical speciation in a tropical rainforest:variation with season, height, and time of dayat the Amazon Tall Tower Observatory (ATTO)

NASA Astrophysics Data System (ADS)

María Yáñez-Serrano, Ana; Nölscher, Anke Christine; Bourtsoukidis, Efstratios; Gomes Alves, Eliane; Ganzeveld, Laurens; Bonn, Boris; Wolff, Stefan; Sa, Marta; Yamasoe, Marcia; Williams, Jonathan; Andreae, Meinrat O.; Kesselmeier, Jürgen

2018-03-01

Speciated monoterpene measurements in rainforest air are scarce, but they are essential for understanding the contribution of these compounds to the overall reactivity of volatile organic compound (VOC) emissions towards the main atmospheric oxidants, such as hydroxyl radicals (OH), ozone (O3) and nitrate radicals (NO3). In this study, we present the chemical speciation of gas-phase monoterpenes measured in the tropical rainforest at the Amazon Tall Tower Observatory (ATTO, Amazonas, Brazil). Samples of VOCs were collected by two automated sampling systems positioned on a tower at 12 and 24 m height and analysed using gas chromatography-flame ionization detection. The samples were collected in October 2015, representing the dry season, and compared with previous wet and dry season studies at the site. In addition, vertical profile measurements (at 12 and 24 m) of total monoterpene mixing ratios were made using proton-transfer-reaction mass spectrometry. The results showed a distinctly different chemical speciation between day and night. For instance, α-pinene was more abundant during the day, whereas limonene was more abundant at night. Reactivity calculations showed that higher abundance does not generally imply higher reactivity. Furthermore, inter- and intra-annual results demonstrate similar chemodiversity during the dry seasons analysed. Simulations with a canopy exchange modelling system show simulated monoterpene mixing ratios that compare relatively well with the observed mixing ratios but also indicate the necessity of more experiments to enhance our understanding of in-canopy sinks of these compounds.

Sulfur speciation and sulfide oxidation in the water column of the Black Sea

NASA Astrophysics Data System (ADS)

Luther, George W., III; Church, Thomas M.; Powell, David

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on storage onboard ship even though they were filtered (0.2 μm) and handled to exclude oxygen contamination. Chemical additives such as formaldehyde, glutaraldehyde, hydroxylamine and ascorbic acid prevented or retarded the sulfide loss. Thiosulfate and azide did not inhibit sulfide loss. These studies suggest an anaerobic chemical oxidation of sulfide rather than a biological oxidation on stored and filtered samples.

Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siebecker, Matthew G.; Chaney, Rufus L.; Sparks, Donald L.

2017-07-01

Serpentine soils have elevated concentrations of trace metals including nickel, cobalt, and chromium compared to non-serpentine soils. Identifying the nickel bearing minerals allows for prediction of potential mobility of nickel. Synchrotron-based techniques can identify the solid-phase chemical forms of nickel with minimal sample treatment. Element concentrations are known to vary among soil particle sizes in serpentine soils. Sonication is a useful method to physically disperse sand, silt and clay particles in soils. Synchrotron-based techniques and sonication were employed to identify nickel species in discrete particle size fractions in several serpentine (ultramafic) topsoils to better understand solid-phase nickel geochemistry. Nickel commonlymore » resided in primary serpentine parent material such as layered-phyllosilicate and chain-inosilicate minerals and was associated with iron oxides. In the clay fractions, nickel was associated with iron oxides and primary serpentine minerals, such as lizardite. Linear combination fitting (LCF) was used to characterize nickel species. Total metal concentration did not correlate with nickel speciation and is not an indicator of the major nickel species in the soil. Differences in soil texture were related to different nickel speciation for several particle size fractionated samples. A discussion on LCF illustrates the importance of choosing standards based not only on statistical methods such as Target Transformation but also on sample mineralogy and particle size. Results from the F-test (Hamilton test), which is an underutilized tool in the literature for LCF in soils, highlight its usefulness to determine the appropriate number of standards to for LCF. EXAFS shell fitting illustrates that destructive interference commonly found for light and heavy elements in layered double hydroxides and in phyllosilicates also can occur in inosilicate minerals, causing similar structural features and leading to false positive results in LCF.« less

Chemical speciation and mobilization of copper and zinc in naturally contaminated mine soils with citric and tartaric acids.

PubMed

Pérez-Esteban, Javier; Escolástico, Consuelo; Moliner, Ana; Masaguer, Alberto

2013-01-01

A one-step extraction procedure and a leaching column experiment were performed to assess the effects of citric and tartaric acids on Cu and Zn mobilization in naturally contaminated mine soils to facilitate assisted phytoextraction. A speciation modeling of the soil solution and the metal fractionation of soils were performed to elucidate the chemical processes that affected metal desorption by organic acids. Different extracting solutions were prepared, all of which contained 0.01 M KNO(3) and different concentrations of organic acids: control without organic acids, 0.5 mM citric, 0.5 mM tartaric, 10 mM citric, 10 mM tartaric, and 5 mM citric +5 mM tartaric. The results of the extraction procedure showed that higher concentrations of organic acids increased metal desorption, and citric acid was more effective at facilitating metal desorption than tartaric acid. Metal desorption was mainly influenced by the decreasing pH and the dissolution of Fe and Mn oxides, not by the formation of soluble metal-organic complexes as was predicted by the speciation modeling. The results of the column study reported that low concentrations of organic acids did not significantly increase metal mobilization and that higher doses were also not able to mobilize Zn. However, 5-10 mM citric acid significantly promoted Cu mobilization (from 1 mg kg(-1) in the control to 42 mg kg(-1) with 10 mM citric acid) and reduced the exchangeable (from 21 to 3 mg kg(-1)) and the Fe and Mn oxides (from 443 to 277 mg kg(-1)) fractions. Citric acid could efficiently facilitate assisted phytoextraction techniques. Copyright © 2012 Elsevier Ltd. All rights reserved.

Flotation as a remediation technique for heavily polluted dredged material. 2. Characterisation of flotated fractions.

PubMed

Cauwenberg, P; Verdonckt, F; Maes, A

1998-01-19

The particle size distribution and the metal speciation of the heavy metals were investigated on dredged sediment and on the fractions obtained by mechanical agitated (Denver) flotation. The transition metal ions (cadmium, copper, lead and zinc) were flotated specifically independent of the particle size. Particle size analysis, EDTA extraction and sequential extracts indicated that during flotation a redistribution of metals occurred due to the oxidation of metal sulphides. This oxidation process was more pronounced when the flotation was performed at higher pH values and resulted in a decrease in flotation specificity.

The ecology of arsenic

USGS Publications Warehouse

Oremland, Ronald S.; Stolz, John F.

2003-01-01

Arsenic is a metalloid whose name conjures up images of murder. Nonetheless, certain prokaryotes use arsenic oxyanions for energy generation, either by oxidizing arsenite or by respiring arsenate. These microbes are phylogenetically diverse and occur in a wide range of habitats. Arsenic cycling may take place in the absence of oxygen and can contribute to organic matter oxidation. In aquifers, these microbial reactions may mobilize arsenic from the solid to the aqueous phase, resulting in contaminated drinking water. Here we review what is known about arsenic-metabolizing bacteria and their potential impact on speciation and mobilization of arsenic in nature.

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River.

PubMed

Hoque, Raza Rafiqul; Goswami, K G; Kusre, B C; Sarma, K P

2011-06-01

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe-Mn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.

Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

PubMed

Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

2013-03-22

Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food. Copyright © 2013 Elsevier B.V. All rights reserved.

Specific extraction of chromium as tetrabutylammonium-chromate and spectrophotometric determination by diphenylcarbazide: speciation of chromium in effluent streams.

PubMed

Noroozifar, M; Khorasani-Motlagh, M

2003-05-01

A very specific, selective, simple, and inexpensive procedure was developed for the speciation of CrVI and CrIII. This method is based on the quantitative extraction of chromate and CrIII (previously oxidized to CrVI) as a tetrabutylammonium-chromate ion-pair in methyl isobutyl ketone (MIBK), and then back extraction and preconcentration with an acidic diphenylcarbazide (DPC) solution. Back extraction was applied to achieve further preconcentration by a final factor of 20. The CrVI-DPC complex was determined in back-extract by a spectrophotometer at 548 nm. Under these extraction conditions, most of the probable concomitant cations and anions remained in the first inorganic phase. The calibration curve was linear up to 0.14 microg L(-1) of CrVI with a detection limit of 2.22 ng L(-1). The developed procedure was found to be suitable for the determination of the CrVI and CrIII species in various natural water samples with a relative standard deviation of better than 1.6%. The method was successfully applied to the speciation of chromium in spiked natural water samples, and also samples of effluent from a leather treatment plant.

Soft X-ray spectromicroscopy for speciation, quantitation and nano-eco-toxicology of nanomaterials.

PubMed

Lawrence, J R; Swerhone, G D W; Dynes, J J; Korber, D R; Hitchcock, A P

2016-02-01

There is a critical need for methods that provide simultaneous detection, identification, quantitation and visualization of nanomaterials at their interface with biological and environmental systems. The approach should allow speciation as well as elemental analysis. Using the intrinsic X-ray absorption properties, soft X-ray scanning transmission X-ray spectromicroscopy (STXM) allows characterization and imaging of a broad range of nanomaterials, including metals, oxides and organic materials, and at the same time is able to provide detailed mapping of biological components. Thus, STXM offers considerable potential for application to research on nanomaterials in biology and the environment. The potential and limitations of STXM in this context are discussed using a range of examples, focusing on the interaction of nanomaterials with microbial cells, biofilms and extracellular polymers. The studies outlined include speciation and mapping of metal-containing nanomaterials (Ti, Ni, Cu) and carbon-based nanomaterials (multiwalled carbon nanotubes, C60 fullerene). The benefits of X-ray fluorescence detection in soft X-ray STXM are illustrated with a study of low levels of Ni in a natural river biofilm. © 2014 The Authors Journal of Microscopy © 2014 Royal Microscopical Society.

Speciation of sulfur from filamentous microbial mats from sulfidic cave springs using X-ray absorption near-edge spectroscopy.

PubMed

Engel, Annette Summers; Lichtenberg, Henning; Prange, Alexander; Hormes, Josef

2007-04-01

Most transformations within the sulfur cycle are controlled by the biosphere, and deciphering the abiotic and biotic nature and turnover of sulfur is critical to understand the geochemical and ecological changes that have occurred throughout the Earth's history. Here, synchrotron radiation-based sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to examine sulfur speciation in natural microbial mats from two aphotic (cave) settings. Habitat geochemistry, microbial community compositions, and sulfur isotope systematics were also evaluated. Microorganisms associated with sulfur metabolism dominated the mats, including members of the Epsilonproteobacteria and Gammaproteobacteria. These groups have not been examined previously by sulfur K-edge XANES. All of the mats consisted of elemental sulfur, with greater contributions of cyclo-octasulfur (S8) compared with polymeric sulfur (Smicro). While this could be a biological fingerprint for some bacteria, the signature may also indicate preferential oxidation of Smicro and S8 accumulation. Higher sulfate content correlated to less S8 in the presence of Epsilonproteobacteria. Sulfur isotope compositions confirmed that sulfur content and sulfur speciation may not correlate to microbial metabolic processes in natural samples, thereby complicating the interpretation of modern and ancient sulfur records.

Bioavailability of particle-associated Se to the bivalve Potamocorbula amurensis

USGS Publications Warehouse

Schlekat, C.E.; Dowdle, P.R.; Lee, B.-G.; Luoma, S.N.; Oremland, R.S.

2000-01-01

Elemental selenium, Se(0), is a prevalent chemical form in sediments, but little is known about its bioavailability. We evaluated the bioavailability of two forms of Se(0) by generating radioisotopic 75Se(0) through bacterial dissimilatory reduction of 75SeO32- by pure bacterial cultures (SES) and by an anaerobic sediment microbial consortium (SED). A third form was generated by reducing 75SeO32- with ascorbic acid (AA). Speciation determinations showed that AA and SES were >90% Se(0), but SED showed a mixture of Se(0), selenoanions, and a residual fraction. Pulse-chase techniques were used to measure assimilation efficiencies (AE) of these particulate Se forms by the bivalve Potamocorbula amurensis. Mean AE values were 3 ?? 2% for AA, 7 ?? 1% for SES, and 28 ?? 15% for SED, showing that the bioavailability of reduced, particle-associated Se is dependent upon its origin. To determine if oxidative microbial processes increased Se transfer, SES 75Se(0) was incubated with an aerobic sediment microbial consortium. After 113 d of incubation, 36% of SES Se(0) was oxidized to SeO32-. Assimilation of total particulate Se was unaffected however (mean AE = 5.5%). The mean AE from the diatom Phaeodactylum tricornutum was 58 ?? 8%, verifying the importance of Se associated with biogenic particles. Speciation and AE results from SED suggest that selenoanion reduction in wetlands and estuaries produces biologically available reduced selenium.Elemental selenium, Se(0), is a prevalent chemical form in sediments, but little is known about its bioavailability. We evaluated the bioavailability of two forms of Se(0) by generating radioisotopic 75Se(0) through bacterial dissimilatory reduction of 75SeO32- by pure bacterial cultures (SES) and by an anaerobic sediment microbial consortium (SED). A third form was generated by reducing 75SeO32 with ascorbic acid (AA). Speciation determinations showed that AA and SES were > 90% Se(0), but SED showed a mixture of Se(0), selenoanions, and a residual fraction. Pulse-chase techniques were used to measure assimilation efficiencies (AE) of these particulate Se forms by the bivalve Potamocorbula amurensis. Mean AE values were 3 ?? 2% for AA, 7 ?? 1% for SES, and 28 ?? 15% for SED, showing that the bioavailability of reduced, particle-associated Se is dependent upon its origin. To determine if oxidative microbial processes increased Se transfer, SES 75Se(0) was incubated with an aerobic sediment microbial consortium. After 113 d of incubation, 36% of SES Se(0) was oxidized to SeO32-. Assimilation of total particulate Se was unaffected however (mean AE = 5.5%). The mean AE from the diatom Phaeodactylum tricornutum was 58 ?? 8%, verifying the importance of Se associated with biogenic particles. Speciation and AE results from SED suggest that selenoanion reduction in wetlands and estuaries produces biologically available reduced selenium.

Selenium analysis in waters. Part 2: Speciation methods.

PubMed

LeBlanc, Kelly L; Kumkrong, Paramee; Mercier, Patrick H J; Mester, Zoltán

2018-06-21

In aquatic ecosystems, there is often no correlation between the total concentration of selenium present in the water column and the toxic effects observed in that environment. This is due, in part, to the variation in the bioavailability of different selenium species to organisms at the base of the aquatic food chain. The first part of this review (Kumkrong et al., 2018) discusses regulatory framework and standard methodologies for selenium analysis in waters. In this second article, we are reviewing the state of speciation analysis and importance of speciation data for decision makers in industry and regulators. We look in detail at fractionation methods for speciation, including the popular selective sequential hydride generation. We examine advantages and limitations of these methods, in terms of achievable detection limits and interferences from other matrix species, as well as the potential to over- or under-estimate operationally-defined fractions based on the various conversion steps involved in fractionation processes. Additionally, we discuss methods of discrete speciation (through separation methods), their importance in analyzing individual selenium species, difficulties associated with their implementation, as well as ways to overcome these difficulties. We also provide a brief overview of biological treatment methods for the remediation of selenium-contaminated waters. We discuss the importance of selenium speciation in the application of these methods and their potential to actually increase the bioavailability of selenium despite decreasing its total waterborne concentration. Copyright © 2018. Published by Elsevier B.V.

Arsenic in ground-water under oxidizing conditions, south-west United States

USGS Publications Warehouse

Robertson, F.N.

1989-01-01

Concentrations of dissolved arsenic in ground-water in alluvial basins of Arizona commonly exceed 50 ??g L-1 and reach values as large as 1,300 ??g L-1. Arsenic speciation analyses show that arsenic occurs in the fully oxidized state of plus 5 (As+5), most likely in the form of HAsO4???2, under existing oxidizing and pH conditions. Arsenic in source areas presumably is oxidized to soluble As before transport into the basin or, if after transport, before burial. Probable sources of arsenic are the sulphide and arsenide deposits in the mineralized areas of the mountains surrounding the basins. Arsenic content of alluvial material ranged from 2 to 88 ppm. Occurrence and removal of arsenic in ground-water are related to the pH and the redox condition of the ground-water, the oxidation state of arsenic, and sorption or exchange. Within basins, dissolved arsenic correlates (P<0.01) with dissolved molybdenum, selenium, vanadium, and fluoride and with pH, suggesting sorption of negative ions. The sorption hypothesis is further supported by enrichment of teachable arsenic in the basin-fill sediments by about tenfold relative to the crustal abundance and by as much as a thousandfold relative to concentrations found in ground-water. Silicate hydrolysis reactions, as defined within the alluvial basins, under closed conditions cause increases in pH basinward and would promote desorption. Within the region, large concentrations of arsenic are commonly associated with the central parts of basins whose chemistries evolve under closed conditions. Arsenic does not correlate with dissolved iron (r = 0.09) but may be partly controlled by iron in the solid phase. High solid-phase arsenic contents were found in red clay beds. Large concentrations of arsenic also were found in water associated with red clay beds. Basins that contain the larger concentrations are bounded primarily by basalt and andesite, suggesting that the iron content as well as the arsenic content of the basin fill may play a role in the occurrence of arsenic in ground-water. Under oxidizing conditions in Arizona, arsenic in ground-water appears to be controlled in part by sorption or desorption of HAsO4???2 on active ferric oxyhydroxide surfaces. ?? 1989 Sciences and Technology Letters.

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

The chapter summarizes the state of knowledge about a metal transport in two-phase system. The first part of this review focuses on the distribution law and main factors determination in classical solvent extraction (solubility and polarity of the solute, as well as inter- and intramolecules interaction. Next part of the chapter is devoted to the reactive solvent extraction and the molecular modeling requiring knowledge on type of extractants, complexation mechanisms, metals ions speciation and oxidation during complexes forming, and other parameters that enable to understand the extraction process. Also the kinetic data that is needed for proper modeling, simulation and design of processes needed for critical separations are discussed. Extraction at liquid-solid system using solvent impregnated resins is partially identical as in the case of the corresponding solvent extraction, therefore this subject was also presented in all aspects of separation process (equilibrium, mechanism, kinetics).

A relatively reduced Hadean continental crust

NASA Astrophysics Data System (ADS)

Yang, Xiaozhi; Gaillard, Fabrice; Scaillet, Bruno

2014-05-01

Among the physical and chemical parameters used to characterize the Earth, oxidation state, as reflected by its prevailing oxygen fugacity (fO2), is a particularly important one. It controls many physicochemical properties and geological processes of the Earth's different reservoirs, and affects the partitioning of elements between coexisting phases and the speciation of degassed volatiles in melts. In the past decades, numerous studies have been conducted to document the evolution of mantle and atmospheric oxidation state with time and in particular the possible transition from an early reduced state to the present oxidized conditions. So far, it has been established that the oxidation state of the uppermost mantle is within ±2 log units of the quartz-fayalite-magnetite (QFM) buffer, probably back to ~4.4 billion years ago (Ga) based on trace-elements studies of mantle-derived komatiites, kimberlites, basalts, volcanics and zircons, and that the O2 levels of atmosphere were initially low and rose markedly ~2.3 Ga known as the Great Oxidation Event (GOE), progressively reaching its present oxidation state of ~10 log units above QFM. In contrast, the secular evolution of oxidation state of the continental crust, an important boundary separating the underlying upper mantle from the surrounding atmosphere and buffering the exchanges and interactions between the Earth's interior and exterior, has rarely been addressed, although the presence of evolved crustal materials on the Earth can be traced back to ~4.4 Ga, e.g. by detrital zircons. Zircon is a common accessory mineral in nature, occurring in a wide variety of igneous, sedimentary and metamorphic rocks, and is almost ubiquitous in crustal rocks. The physical and chemical durability of zircons makes them widely used in geochemical studies in terms of trace-elements, isotopes, ages and melt/mineral inclusions; in particular, zircons are persistent under most crustal conditions and can survive many secondary processes such as metamorphism, weathering and erosion. Thus, zircons in granites of shallow crust may record the chemical/isotopic composition of the deep crust that is otherwise inaccessible, and offer robust records of the magmatic and crust-forming events preserved in the continental crust. In fact, due to the absence of suitable rock records (in particular for periods older than ~4.0 Ga), studies in recent years concerning the nature, composition, growth and evolution of the continental crust, and especially the Hadean crust, have heavily relied on inherited/detrital zircons. Natural igneous zircons incorporate rare-earth elements (REE) and other trace elements in their structure at concentrations controlled by the temperature, pressure, fO2 and composition of their crystallization environment. Petrological observations and recent experiments have shown that the concentration of Ce relative to other REE in igneous zircons can be used to constrain the fO2 during their growth. By combining available trace-elements data of igneous zircons of crustal origin, we show that the Hadean continental crust was significantly more reduced than its modern counterpart and experienced progressive oxidation till ~3.6 billions years ago. We suggest that the increase in the oxidation state of the Hadean continental crust is related to the progressive decline in the intensity of meteorite impacts during the late veneer. Impacts of carbon- and hydrogen-rich materials during the formation of Hadean granitic crust must have favoured strongly reduced magmatism. The conjunction of cold, wet and reduced granitic magmatism during the Hadean implies the degassing of methane and water. When impacts ended, magma produced by normal decompression melting of the mantle imparted more oxidizing conditions to erupted lavas and the related crust.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neu, Mary Patricia

The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK as and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK a = 5.94, logβ 120 = 10.92; acetohydroxamic acid, pK a = 9.34, logβ 120 = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinatemore » geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is logβ 120 = 41.7. The solubility limited speciation of 242Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods.« less

Characterization of typical metal particles during haze episodes in Shanghai, China.

PubMed

Li, Rui; Yang, Xin; Fu, Hongbo; Hu, Qingqing; Zhang, Liwu; Chen, Jianmin

2017-08-01

Aerosol particles were collected during three heavy haze episodes at Shanghai in the winter of 2013. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy was used to study the morphology and speciation of typical metal particles at a single-particle level. In addition, time-of-flight aerosol mass spectrometry (ATOFMS) was applied to identify the speciation of the Fe-containing particles. TEM analysis indicated that various metal-containing particles were hosted by sulfates, nitrates, and oxides. Fe-bearing particles mainly originated from vehicle emissions and/or steel production. Pb-, Zn-, and Sb-bearing particles were mainly contributed by anthropogenic sources. Fe-bearing particles were clustered into six groups by ATOFMS: Fe-Carbon, Fe-Inorganic, Fe-Trace metal, Fe-CN, Fe-PO 3, and Fe-NO 3 . ATOFMS data suggested that Fe-containing particles corresponded to different origins, including industrial activities, resuspension of dusts, and vehicle emissions. Fe-Carbon and Fe-CN particles displayed significant diurnal variation, and high levels were observed during the morning rush hours. Fe-Inorganic and Fe-Trace metal particle levels peaked at night. Furthermore, Fe-Carbon and Fe-PO 3 were mainly concentrated in the fine particles. Fe-CN, Fe-Inorganic, and Fe-Trace metal exhibited bimodal distribution. The mixing state of the particles revealed that all Fe-bearing particles tended to be mixed with sulfate and nitrate. The data presented herein is essential for elucidating the origin, evolution processes, and health effects of metal-bearing particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isotopic Composition of Gaseous Elemental Mercury in the Free Troposphere of the Pic du Midi Observatory, France.

PubMed

Fu, Xuewu; Marusczak, Nicolas; Wang, Xun; Gheusi, François; Sonke, Jeroen E

2016-06-07

Understanding the sources and transformations of mercury (Hg) in the free troposphere is a critical aspect of global Hg research. Here we present one year of observations of atmospheric Hg speciation and gaseous elemental Hg (GEM) isotopic composition at the high-altitude Pic du Midi Observatory (2860 m above sea level) in France. Biweekly integrated GEM from February 2012 to January 2013 revealed significant variations in δ(202)HgGEM (-0.04‰ to 0.52‰) but not in Δ(199)HgGEM (-0.17‰ to -0.27‰) or Δ(200)HgGEM (-0.10‰ to 0.05‰). δ(202)HgGEM was negatively correlated with CO and reflected air mass origins from Europe (high CO, low δ(202)HgGEM) and from the Atlantic Ocean (low CO, high δ(202)HgGEM). We suggest that the δ(202)HgGEM variations represent mixing of recent low δ(202)HgGEM European anthropogenic emissions with high δ(202)HgGEM northern hemispheric background GEM. In addition, Atlantic Ocean free troposphere air masses showed a positive correlation between δ(202)HgGEM and gaseous oxidized Hg (GOM) concentrations, indicative of mass-dependent Hg isotope fractionation during GEM oxidation. On the basis of atmospheric δ(202)HgGEM and speciated Hg observations, we suggest that the oceanic free troposphere is a reservoir within which GEM is readily oxidized to GOM.

Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Miracolo, M. A.; Presto, A. A.; Adams, P. J.; Robinson, A. L.

2012-04-01

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of low-volatility organics (semi-volatile and intermediate volatility organic compounds). The model is parameterized and tested using SOA data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. Photo-oxidation formed a significant amount of SOA, much of which cannot be explained based on the emissions of traditional, speciated precursors; we refer to this as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of low-volatility organic vapors measured using sorbents. Since these vapors could not be speciated, we employ a volatility-based approach to model NT-SOA formation. We show that the method proposed by Robinson et al. (2007) is unable to explain the timing of NT-SOA formation because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast, a Hybrid method, similar to models of traditional SOA formation, assumes a larger reduction in volatility with each oxidation step and results in a better reproduction of NT-SOA formation. The NT-SOA yields estimated for the low-volatility organic vapor emissions are similar to literature data for large n-alkanes and other low-volatility organics. The yields vary with fuel composition (JP8 versus Fischer-Tropsch) and engine load (idle versus non-idle). These differences are consistent with the expected contribution of high (aromatics and n-alkanes) and low (branched alkanes and oxygenated species) SOA forming species to the exhaust.

Validation of an updated fractionation and indirect speciation procedure for inorganic arsenic in oxic and suboxic soils and sediments.

PubMed

Lock, Alan; Wallschläger, Dirk; McMurdo, Colin; Tyler, Laura; Belzile, Nelson; Spiers, Graeme

2016-12-01

A sequential extraction procedure (SEP) for the speciation analysis of As(III) and As(V) in oxic and suboxic soils and sediments was validated using a natural lake sediment and three certified reference materials, as well as spike recoveries of As(III) and As(V). Many of the extraction steps have been previously validated making the procedure useful for comparisons to similar previous SEP studies. The novel aspect of this research is the validation for the SEP to maintain As(III) and As(V) species. The proposed five step extraction procedure includes the extraction agents (NH 4 ) 2 SO 4 , NH 4 H 2 PO 4 , H 3 PO 4  + NH 2 OH·HCl, oxalate + ascorbic acid (heated), and HNO 3  + HCl + HF, targeting operationally defined easily exchangeable, strongly sorbed, amorphous Fe oxide bound, crystalline Fe oxide bound, and residual As fractions, respectively. The third extraction step, H 3 PO 4  + NH 2 OH·HCl, has not been previously validated for fraction selectivity. We present evidence for this extraction step to target As complexed with amorphous Fe oxides when used in the SEP proposed here. All solutions were analyzed on ICP-MS. The greatest concentrations of As were extracted from the amorphous Fe oxide fraction and the dominant species was As(V). Lake sediment materials were found to have higher As(III) concentrations than the soil materials. Because different soils/sediments have different chemical characteristics, maintenance of As species during extractions must be validated for specific soil/sediment types using spiking experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Environmental and health impacts of fine and ultrafine metallic particles: Assessment of threat scores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goix, Sylvaine; UMR 5245 CNRS-INP-UPS, EcoLab; Lévêque, Thibaut

2014-08-15

This study proposes global threat scores to prioritize the harmfulness of anthropogenic fine and ultrafine metallic particles (FMP) emitted into the atmosphere at the global scale. (Eco)toxicity of physicochemically characterized FMP oxides for metals currently observed in the atmosphere (CdO, CuO, PbO, PbSO{sub 4}, Sb{sub 2}O{sub 3}, and ZnO) was assessed by performing complementary in vitro tests: ecotoxicity, human bioaccessibility, cytotoxicity, and oxidative potential. Using an innovative methodology based on the combination of (eco)toxicity and physicochemical results, the following hazard classification of the particles is proposed: CdCl{sub 2}∼CdO>CuO>PbO>ZnO>PbSO{sub 4}>Sb{sub 2}O{sub 3}. Both cadmium compounds exhibited the highest threat score duemore » to their high cytotoxicity and bioaccessible dose, whatever their solubility and speciation, suggesting that cadmium toxicity is due to its chemical form rather than its physical form. In contrast, the Sb{sub 2}O{sub 3} threat score was the lowest due to particles with low specific area and solubility, with no effects except a slight oxidative stress. As FMP physicochemical properties reveal differences in specific area, crystallization systems, dissolution process, and speciation, various mechanisms may influence their biological impact. Finally, this newly developed and global approach could be widely used in various contexts of pollution by complex metal particles and may improve risk management. - Highlights: • Seven micro- and nano- monometallic characterized particles were studied as references. • Bioaccessibility, eco and cytotoxicity, and oxidative potential assays were performed. • According to calculated threat scores: CdCl{sub 2}∼CdO>CuO>PbO>ZnO>PbSO{sub 4}>Sb{sub 2}O{sub 3}.« less

Actinide Solubility and Speciation in the WIPP [PowerPoint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, Donald T.

2015-11-02

The presentation begins with the role and need for nuclear repositories (overall concept, international updates (Sweden, Finland, France, China), US approach and current status), then moves on to the WIPP TRU repository concept (design, current status--safety incidents of February 5 and 14, 2014, path forward), and finally considers the WIPP safety case: dissolved actinide concentrations (overall approach, oxidation state distribution and redox control, solubility of actinides, colloidal contribution and microbial effects). The following conclusions are set forth: (1) International programs are moving forward, but at a very slow and somewhat sporadic pace. (2) In the United States, the Salt repositorymore » concept, from the perspective of the long-term safety case, remains a viable option for nuclear waste management despite the current operational issues/concerns. (3) Current model/PA prediction (WIPP example) are built on redundant conservatisms. These conservatisms are being addressed in the ongoing and future research to fill existing data gaps--redox control of plutonium by Fe(0, II), thorium (analog) solubility studies in simulated brine, contribution of intrinsic and biocolloids to the mobile concentration, and clarification of microbial ecology and effects.« less

THERMODYNAMIC REACTION CONSTANTS FOR MODELING AQUEOUS ENVIRONMENTAL MERCURY SPECIATION

EPA Science Inventory

Unacceptably high fish tissue mercury residues are responsible for the majority of fish consumption advisories issued in 48 states of the United States of America. Mercury also has emerged as a transboundary contaminant of global concern. Although monomethylmercury is generally...

Speciation dynamics in the SE Asian tropics: Putting a time perspective on the phylogeny and biogeography of Sundaland tree squirrels, Sundasciurus.

PubMed

den Tex, Robert-Jan; Thorington, Richard; Maldonado, Jesus E; Leonard, Jennifer A

2010-05-01

Tropical rainforests are well known for their extraordinarily high levels of biodiversity. The origin of this species richness is still debated. For instance, the museum hypothesis states that over evolutionary time more and more species will accumulate with relatively few extinctions. In contrast, the Pleistocene diversification model argues that during the last 2 million years, climatic factors (glaciations) caused environmental changes that drove isolation and vicariant speciation events. In this study, we construct a molecular phylogeny of the Sundaland (Malay Peninsula, Sumata, Borneo, Palawan) and Greater Mindanao (Mindanao, Samar, Leyte) tree squirrels (genus Sundasciurus). Our results show that most speciation events in this forest dependent taxon occurred before the Pleistocene and that even the timing of intra-specific splits among populations from different landmasses are relatively old. Additionally, we found unexpectedly high divergence within and between highland populations of S. tenuis on Sumatra and the Malay Peninsula, highlighting the importance of Pliocene events in both speciation and within species divergences in this region. Copyright 2010 Elsevier Inc. All rights reserved.

Thermodynamic behavior of a phase transition in a model for sympatric speciation

NASA Astrophysics Data System (ADS)

Luz-Burgoa, K.; Moss de Oliveira, S.; Schwämmle, Veit; Sá Martins, J. S.

2006-08-01

We investigate the macroscopic effects of the ingredients that drive the origin of species through sympatric speciation. In our model, sympatric speciation is obtained as we tune up the strength of competition between individuals with different phenotypes. As a function of this control parameter, we can characterize, through the behavior of a macroscopic order parameter, a phase transition from a nonspeciation to a speciation state of the system. The behavior of the first derivative of the order parameter with respect to the control parameter is consistent with a phase transition and exhibits a sharp peak at the transition point. For different resources distribution, the transition point is shifted, an effect similar to pressure in a PVT system. The inverse of the parameter related to a sexual selection strength behaves like an external field in the system and, as thus, is also a control parameter. The macroscopic effects of the biological parameters used in our model are a reminiscent of the behavior of thermodynamic quantities in a phase transition of an equilibrium physical system.

[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.

The redox processes in Hg-contaminated soils from Descoberto (Minas Gerais, Brazil): implications for the mercury cycle.

PubMed

Windmöller, Cláudia C; Durão Júnior, Walter A; de Oliveira, Aline; do Valle, Cláudia M

2015-02-01

Investigations of the redox process and chemical speciation of Hg(II) lead to a better understanding of biogeochemical processes controlling the transformation of Hg(II) into toxic and bioaccumulative monomethyl mercury, mainly in areas contaminated with Hg(0). This study investigates the speciation and redox processes of Hg in soil samples from a small area contaminated with Hg(0) as a result of gold mining activities in the rural municipality of Descoberto (Minas Gerais, Brazil). Soil samples were prepared by adding Hg(0) and HgCl2 separately to dry soil, and the Hg redox process was monitored using thermodesorption coupled to atomic absorption spectrometry. A portion of the Hg(0) added was volatilized (up to 37.4±2.0%) or oxidized (from 36±7% to 88±16%). A correlation with Mn suggests that this oxidation is favored, but many other factors must be evaluated, such as the presence of microorganisms and the types of organic matter present. The interaction of Hg with the matrix is suggested to involve Hg(II)-complexes formed with inorganic and organic sulfur ligands and/or nonspecific adsorption onto oxides of Fe, Al and/or Mn. The kinetics of the oxidation reaction was approximated for two first-order reactions; the faster reaction was attributed to the oxidation of Hg(0)/Hg(I), and the slower reaction corresponded to Hg(I)/Hg(II). The second stage was 43-139 times slower than the first. The samples spiked with Hg(II) showed low volatilization and a shifting of the signal of Hg(II) to lower temperatures. These results show that the extent, rate and type of redox process can be adverse in soils. Descoberto can serve as an example for areas contaminated with Hg(0). Copyright © 2014 Elsevier Inc. All rights reserved.

A REVIEW AND SYNTHESIS OF MONOTERPENE SPECIATION FROM FORESTS IN THE UNITED STATES

EPA Science Inventory

The monoterpene composition (emission and tissue internal concentration) of major forest tree species in the United States is discussed. Of the 14 most commonly occurring compounds ( -pinene, -pinene, 3-carene, d-limonene, camphene, myrcene, -terpinenen, -phellandrene, sabin...

Aniline chlorination by in situ formed Ag-Cl complexes under simulated solar light irradiation.

PubMed

Hu, Xuefeng; Wang, Xiaowen; Dong, Liuliu; Chang, Fei; Luo, Yongming

2015-01-01

Ag speciation in a chloride medium was dependent upon the Cl/Ag ratio after releasing into surface water. In this study, the photoreaction of in situ formed Ag-Cl species and their effects on aniline photochlorination were systematically investigated. Our results suggested that formation of chloroaniline was strongly relevant to the Cl/Ag ratio and could be interpreted using the thermodynamically expected speciation of Ag in the presence of Cl-. AgCl was the main species responsible for the photochlorination of aniline. Both photoinduced hole and •OH drove the oxidation of Cl- to radical •Cl, which promoted the chlorination of aniline. Ag0 formation was observed from the surface plasmon resonance absorption during AgCl photoreaction. This study revealed that Ag+ released into Cl--containing water may result in the formation of chlorinated intermediates of organic compounds under solar light irradiation.

Speciation of strontium-90 in NIST natural matrix standard reference materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, J.W.L.; Inn, K.G.W.; Garcia, M.E.

1995-12-31

A sequential leaching, radiochemical separating, and low-level beta-particle counting procedure was designed to study the speciation of radionuclides in natural matrix standard reference materials, SRMs 4350B (Columbia River Sediment) and 4353 (Rocky Flats Soil-1). Strontium-90 is the first radionuclide studied because of the difficulty experienced with this nuclide in natural-matrix SRMs. The nine-step procedure extracted {sup 90}Sr from the following fractions: water solubles, exchangeables, carbonates, reducibles, organics, iron and manganese oxides, acid leachables, micas, and silicates. The majority of {sup 90}Sr in the soil samples was found in the exchangeable fraction. By contrast, the {sup 90}Sr in the sediment ismore » more evenly distributed among the various leached fractions. Information on the leach distribution of radionuclides in environmental SRMs, based on the procedure described, should lead to more cost-effective restoration strategies and more confidence in risk assessments of human health hazards.« less

A spectroscopic study for understanding the speciation of Cr on palm shell based adsorbents and their application for the remediation of chrome plating effluents.

PubMed

Kushwaha, Shilpi; Sreedhar, B; Sudhakar, Padmaja P

2012-07-01

Palm shell based adsorbents prepared under five different thermochemical conditions have been shown to be quite effective for removal of chromium (III and VI) from aqueous solutions. X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FT-IR) have been used to determine information about the speciation and binding of chromium on the adsorbents under study. X-ray photoelectron spectroscopy (XPS) studies indicate that oxidation of lignin moieties takes place concurrently to Cr(VI) reduction and leads to the formation of hydroxyl and carboxyl functions. The maximum adsorption capacity for hexavalent chromium was found to be about 313 mg/g in an acidic medium using PAPSP. This is comparable to other natural substrates and ordinary adsorbents. The efficacy of the adsorbents under study to remove chromium from plating waste water has been demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe 5O 6

DOE PAGES

Lavina, Barbara; Meng, Yue

2015-06-26

The iron-oxygen system is the most important reference of rocks’ redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe 4O 5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe 3O 4, and Fe 2O 3. Combining synthesis at high pressure and temperature with micro- diffraction mapping, we have identified yet another distinct iron oxide, Fe 5O 6. The new compound, which has an orthorhombic structure, was obtained in themore » pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe 5O 6, Fe 4O 5, and h-Fe 3O 4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe 5O 6, along with FeO and Fe 4O 5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geo- chemical importance. Here, we are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe 5O 6, Fe 4O 5, and h-Fe 3O 4—in a narrow compositional range (0.75 < Fe/O < 1.0). New, finely spaced oxygen buffers at conditions of the Earth’s mantle can be defined.« less

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

NASA Astrophysics Data System (ADS)

Binder, Bernd; Wenzel, Thomas; Keppler, Hans

2018-02-01

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750-850 °C as a function of oxygen fugacity (Ni-NiO or Re-ReO2 buffer), melt composition (Al/(Na + K) ratio), and fluid composition (NaCl and CO2 content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under "reducing conditions" (Ni-NiO buffer), D fluid/melt is nearly one order of magnitude larger (323 ± 14 for a metaluminous melt) than under "oxidizing conditions" (Re-ReO2 buffer; 74 ± 5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H2S and HS- under reducing conditions and of SO4 2- and HSO4 - under oxidizing conditions, while SO2 is undetectable. The latter observation suggests that already at the Re-ReO2 buffer, sulfur in the fluid is almost completely in the S6+ state and, therefore, more oxidized than expected according to current models. CO2 in the fluid (up to x CO2 = 0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D fluid/melt is independent of x NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H2S to NaSH as dominant sulfur species in the fluid. A decrease of D fluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S6+ state and may remain undetected by conventional methods that only measure SO2. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.

Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

NASA Astrophysics Data System (ADS)

Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

2010-12-01

Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix composition and thermodynamic conditions could facilitate a transformation to more crystalline iron phases and increase metal bioavailability. While preliminary data from in-creek aggregates show no clear trend in mineralogical composition with downstream transport, only the furthest downstream samples have 2-line ferrihydrite in amounts detectable by XRD.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solomon, D.; Lehmann, J; Kinyangi, J

The soil environment is a primary component of the global biogeochemical sulfur (S) cycle, acting as a source and sink of various S species and mediating oxidation state changes. However, ecological significance of the various S forms and the impacts of human intervention and climate on the amount and structural composition of these compounds are still poorly understood. We investigated the long-term influences of anthropogenically mediated transitions from natural to managed ecosystems on molecular-level speciation, biogeochemical dynamics, and the apparent temperature sensitivity of S moieties in temperate, subtropical, and tropical environments with mean annual temperature (MAT) ranging from 5C tomore » 21C, using elemental analysis and X-ray absorption near-edge structure (XANES) spectroscopy. Land-use and land-cover changes led to the depletion of total soil S in all three ecoregions over a period of up to 103 years. The largest decline occurred from tropical forest agroecosystems (67% Kakamega and 76% Nandi, Kenya), compared to losses from temperate (36% at Lethbridge, Canada, and 40% at Pendleton, USA) and subtropical (48% at South Africa) grassland agroecosystems. The total S losses correlated significantly with MAT. Anthropogenic interventions profoundly altered the molecular-level composition and resulted in an apparent shift in oxidation states of organic S from native ecosystems composed primarily of S moieties in intermediate and highly reduced oxidation states toward managed agroecosystems dominated by organic S rich in strongly oxidized functionalities. The most prominent change occurred in thiols and sulfides, the proportion of which decreased by 46% (Lethbridge) and 57% (Pendleton) in temperate agroecosystems, by 46% in subtropical agroecosystems, and by 79% (Nandi) and 81% (Kakamega) in tropical agroecosystems. The proportion of organic S directly linked to O increased by 81%, 168%, 40%, 92%, and 85%, respectively. Among the various organic S functionalities, thiols and sulfides seem to have higher apparent temperature sensitivity, and thus these organic S moieties may become prone to losses due to land-use changes, even from the cooler regions of the world if MAT of these regions rise in the future.« less

The redox state of iron in the matrix of CI, CM and metamorphosed CM chondrites by XANES spectroscopy

NASA Astrophysics Data System (ADS)

Beck, P.; De Andrade, V.; Orthous-Daunay, F.-R.; Veronesi, G.; Cotte, M.; Quirico, E.; Schmitt, B.

2012-12-01

Carbonaceous chondrites record the action of water at some point of their petrological history. These meteorites are usually connected to low albedo asteroid, which present visible/near-IR absorption explained by iron related absorption within phyllosilicates and oxides. In order to obtain quantitative insight into the mineralogy of iron-bearing phases, we have measured X-ray absorption near-edge spectroscopy at the iron K-edge of matrix from carbonaceous chondrites. This method enables to constrain the redox state and environment of iron in these meteorites. For this study, we selected seven CM chondrites and the CI Orgueil, expected to span a range of aqueous alteration degrees. Our analysis of the pre-edge features show that the redox state of Orgueil (CI) is dominated by octahedral Fe and that the Fe3+/(Fe3++Fe2+) atomic ratio is above 80%. Full-inversion of the spectra suggests that the iron budget is dominated by iron oxides, with additional contributions from phyllosilicate. In the case of the CM, the iron speciation appears different that in the case of Orgueil. Cronstedtite is identified from the inversion of the spectra, and suggested by the presence of significant amount of tetrahedral Fe3+. Within the CM chondrites, a trend of aqueous alteration appears presents, and which is roughly correlated to the scheme defined by Rubin et al. (2007). This trend is characterized by an increase in the amount of iron oxides. Two shock metamorphosed CM are present in our dataset (PCA 91008, WIS 91600). If WIS 91600 does not appear distinguishable, from the CM trend, in the case of PCA 91008, shock metamorphism did impact the pre-edge intensity and an increased amount of anhydrous silicates is found. Although the matrix was dehydrated, significant amount of Fe3+ is still present, providing a memory of the aqueous alteration.

Preignition and Autoignition Behavior of the Xylene Isomers

DTIC Science & Technology

2010-03-01

of the carbon-carbon bond at the carbon atom one removed from the radical site (Law, 2006). 10 ketohydroperoxide produces another hydroxyl radical...paraffin, naphthene , and aromatic content of jet fuel samples fairly well (Holley et al., 2007). A more detailed chemical speciation has been...an intermediate from toluene oxidation in the PFR facility. This also removes concern that phenol may have reacted during the quenching process, if

[Evaluation of compounding EDTA and citric acid on remediation of heavy metals contaminated soil].

PubMed

Yin, Xue; Chen, Jia-Jun; Cai, Wen-Min

2014-08-01

As commonly used eluents, Na2EDTA (EDTA) and citric acid (CA) have been widely applied in remediation of soil contaminated by heavy metals. In order to evaluate the removal of arsenic, cadmium, copper, and lead in the contaminated soil collected in a chemical plant by compounding EDTA and CA, a series of stirring experiments were conducted. Furthermore, the changes in speciation distribution of heavy metals before and after washing were studied. The results showed that, adopting the optimal molar ratio of EDTA/CA (1:1), when the pH of the solution was 3, the stirring time was 30 min, the stirring rate was 150 r x min(-1) and the L/S was 5:1, the removal rates of arsenic, cadmium, copper and lead could reach 11.72%, 43.39%, 24.36% and 27.17%, respectively. And it was found that after washing, for arsenic and copper, the content of acid dissolved fraction rose which increased the percentage of available contents. Fe-Mn oxide fraction mainly contributed to the removal of copper. As for cadmium, the percentages of acid dissolved fraction, Fe-Mn oxide fraction and organic fraction also decreased. In practical projects, speciation changes would pose certain environmental risk after soil washing, which should be taken into consideration.

Sequestration of arsenic in ombrotrophic peatlands

NASA Astrophysics Data System (ADS)

Rothwell, James; Hudson-Edwards, Karen; Taylor, Kevin; Polya, David; Evans, Martin; Allott, Tim

2014-05-01

Peatlands can be important stores of arsenic but we are lacking spectroscopic evidence of the sequestration pathways of this toxic metalloid in peatland environments. This study reports on the solid-phase speciation of anthropogenically-derived arsenic in atmospherically contaminated peat from the Peak District National Park (UK). Surface and sub-surface peat samples were analysed by synchrotron X-ray absorption spectroscopy on B18 beamline at Diamond Light Source (UK). The results suggest that there are contrasting arsenic sequestration mechanisms in the peat. The bulk arsenic speciation results, in combination with strong arsenic-iron correlations at the surface, suggest that iron (hydr)oxides are key phases for the immobilisation of arsenic at the peat surface. In contrast, the deeper peat samples are dominated by arsenic sulphides (arsenopyrite, realgar and orpiment). Given that these peats receive inputs solely from the atmosphere, the presence of these sulphide phases suggests an in-situ authigenic formation. Redox oscillations in the peat due to a fluctuating water table and an abundant store of legacy sulphur from historic acid rain inputs may favour the precipitation of arsenic sequestering sulphides in sub-surface horizons. Oxidation-induced loss of these arsenic sequestering sulphur species by water table drawdown has important implications for the mobility of arsenic and the quality of waters draining peatlands.

A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS.

PubMed

Day, Jason A; Montes-Bayón, María; Vonderheide, Anne P; Caruso, Joseph A

2002-08-01

Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate.

Ferric minerals and organic matter change arsenic speciation in copper mine tailings.

PubMed

Wang, Peng; Liu, Yunjia; Menzies, Neal W; Wehr, J Bernhard; de Jonge, Martin D; Howard, Daryl L; Kopittke, Peter M; Huang, Longbin

2016-11-01

Arsenic (As) is commonly associated with Cu ore minerals, with the resultant risk that As can be released offsite from mine tailings. We used synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide in situ, laterally-resolved speciation of As within tailings which differed in magnetite content (5-12%) and organic matter content (0-5%). Although the total As content was lower in tailings with low magnetite (LM), the soluble (pore water) As was actually 7-times higher in LM tailings than in high magnetite (HM) tailings. Additionally, amendment with 5% sugarcane mulch residues (SMR) (for revegetation) further increased soluble As due to the dissolution and oxidation of arsenopyrite or orpiment. Indeed, in HM tailings, arsenopyrite and orpiment initially accounted for 88% of the total As, which decreased to 48% upon the addition of SMR - this being associated with an increase in As V -ferrihydrite from 12% to 52%. In LM tailings, the pattern of As distribution and speciation was similar, with As as As V -ferrihydrite increasing from 57% to 75% upon the addition of SMR. These findings indicate that changes in ore processing technology, such as the recovery of magnetite could have significant environmental consequences regarding the As mobilisation and transformation in mine tailings. Copyright © 2016 Elsevier Ltd. All rights reserved.

Iodine-129 and iodine-127 speciation in groundwater at the Hanford site, US: iodate incorporation into calcite.

PubMed

Zhang, Saijin; Xu, Chen; Creeley, Danielle; Ho, Yi-Fang; Li, Hsiu-Ping; Grandbois, Russell; Schwehr, Kathleen A; Kaplan, Daniel I; Yeager, Chris M; Wellman, Dawn; Santschi, Peter H

2013-09-03

The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounted for up to 84% of the total iodine present. The alkaline pH (pH ∼ 8) and predominantly oxidizing environment may have prevented reduction of the iodate. In addition, groundwater samples were found to have large amounts of calcite precipitate which were likely formed as a result of CO2 degassing during removal from the deep subsurface (>70m depth). Further analyses indicated that between 7 and 40% of the dissolved (127)I and (129)I that was originally in the groundwater had coprecipitated in the calcite. Iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevating the pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of (129)I. Furthermore, the common sampling artifact resulting in the precipitation of calcite by degassing CO2, had the unintended consequence of providing insight into a potential solution for the in situ remediation of groundwater (129)I.

Profiling planktonic biomass using element-specific, multicomponent nuclear magnetic resonance spectroscopy.

PubMed

Komatsu, Takanori; Kobayashi, Toshiya; Hatanaka, Minoru; Kikuchi, Jun

2015-06-02

Planktonic metabolism plays crucial roles in Earth's elemental cycles. Chemical speciation as well as elemental stoichiometry is important for advancing our understanding of planktonic roles in biogeochemical cycles. In this study, a multicomponent solid-state nuclear magnetic resonance (NMR) approach is proposed for chemical speciation of cellular components, using several advanced NMR techniques. Measurements by ssNMR were performed on (13)C and (15)N-labeled Euglena gracilis, a flagellated protist. 3D dipolar-assisted rotational resonance, double-cross-polarization (1)H-(13)C correlation spectroscopy, and (1)H-(13)C solid-state heteronuclear single quantum correlation spectroscopy successively allowed characterization of cellular components. These techniques were then applied to E. gracilis cultured in high and low ammonium media to demonstrate the power of this method for profiling and comparing cellular components. Cellular NMR spectra indicated that ammonium induced both paramylon degradation and amination. Arginine was stored as a nitrogen reserve and ammonium replaced by arginine catabolism via the arginine dihydrolase pathway. (15)N and (31)P cellular ssNMR indicated arginine and polyphosphate accumulation in E. gracilis, respectively. This chemical speciation technique will contribute to environmental research by providing detailed information on environmental chemical properties.

Effect of fO2 on phase relationship in basaltic andesites during magmatic differentiation: Control of fO2 and sulphur speciation in piston cylinder experiments.

NASA Astrophysics Data System (ADS)

Matjuschkin, Vladimir; Tattitch, Brian; Blundy, Jonathan D.; Skora, Susanne

2014-05-01

Within the mantle wedge above subduction zones, oxidation reaction take place by interaction of reduced mantle rocks with more oxidized, hydrous fluids, which can cause a local drop of the solidus, resulting in partial melting (2,6,7). The resultant melts are more oxidized that their ocean floor counterparts, which has implications for their subsequent differentiation paths, the speciation of multivalent elements and the solubility and transport of chemical compounds in magmatic systems (1,4,5). We present a series of sulphur-doped high-pressure experiments conducted to investigate the effect of oxygen fugacity on phase relationships and the behaviour of sulphur in silicate melts. Natural aphyric andesite (FM37) erupted from Laguna del Maule volcano, Chile (3) was selected as a starting composition. Experiments were carried out at 5kbar, 950-1150° C and variable oxygen fugacity conditions. New experiments buffered at Co-CoO and Ni-NiO buffer conditions have been performed using a new "MTB capsule design" developed in order to accurately control fO2 by means of a double capsule containing metal-oxide buffers and a pyrex sleeve to minimise H2 diffusion. This new design constrains oxygen fugacity to within ±0.1-0.2logfO2 units of the target value. Before conducting these experiments, the assemblage was tested multiple times at 10kbar, 1000° C over 24-48 hours and demonstrated consistent, accurate fO2 control. Analyses of the preliminary experimental run products, from a related Chilean basaltic andesite starting composition, demonstrate a clear effect of fO2 on phase relationships and the proportion of melt generated during experiments. Under oxidized conditions, as temperature decreased from 1150° C to 1050° C, the amount of melt decreased from 100% to ~80%, due to the formation of orthopyroxene, anhydrite and plagioclase. In contrast, in reduced runs the system remains nearly liquid (~5% crystals) down to 950° C due to the change in sulphur speciation and onset of orthopyroxene precipitation at much lower temperatures. The change in temperature from 1150 to 950° C resulted in a drop in S content from ~2500ppm to ~1000ppm in the melt for oxidized experiments, whereas S slightly increased from ~3000 to ~3500ppm in the reduced experiments. Quantitative control over fO2 will allow for more precise determination of phase relations and control of sulphur specification, offering a possibility of detailed reconstruction of metals enrichment in silicate melts. Cited references: [1] Botcharnikov et al. (2011) Nature 4:217-230, [2] Foley (2011) J Petrol 52:1363-1391, [3] Frey et al. (1984) CMP 88:133-149, [4] Jenner et al. (2010) J Petrol 51:2445-2464, [5] Jugo et al. (2010) GCA 74:5926-5938, [6] Rohrbach et al. (2007) Nature 449:456-458, [7] Taylor and Green (1988) Nature 332:349-352

[Analysis of washing efficiency and change in lead speciation in lead-contaminated soil of a battery factory].

PubMed

Ren, Bei; Huang, Jin-lou; Miao, Ming-sheng

2013-09-01

Lead-contaminated soil with different pollution load in a lead battery factory in the southwest of China was chosen as the research object, the lead content and speciation were analyzed, and different washing agents were screened. The lead washing efficiency and lead speciation were analyzed under different pH conditions, and the soil of different particle size was washed using different duration to determine the best washing time. The results showed that the soil of sites A and B in the factory was severely contaminated, the lead concentration reaching 15,703.22 mg x kg(-1) and 1747.78 mg x kg(-1), respectively, and the proportion of the active-state lead was relatively high, while the residue state accounted for only 17.32%, 11.64%, 14.6% and 10.2%. EDTA and hydrochloric acid showed the best extraction effect in the 5 washing agents tested, which included EDTA, hydrochloric acid, citric acid, rhamnolipid and SDS. Cleaning under acidic conditions could not only effectively extract the total amount of lead but also effectively reduce the environmental risk of active-state lead. pH 4-7 was suggested as the most appropriate condition. The cleaning effect of coarse sand and fine sand was good, while for washing powder clay, it is better to improve the process, with the optimal washing time determined as 240 min.

Exploring Molecular Speciation and Crystallization Mechanism of Amorphous 2-Phenylamino Nicotinic Acid.

PubMed

Kalra, Arjun; Lubach, Joseph W; Munson, Eric J; Li, Tonglei

2018-02-07

Molecular understanding of phase stability and transition of the amorphous state helps in formulation and manufacturing of poorly-soluble drugs. Crystallization of a model compound, 2-phenylamino nicotinic acid (2PNA), from the amorphous state was studied using solid-state analytical methods. Our previous report suggests that 2PNA molecules mainly develop intermolecular -COOH∙∙∙pyridine N (acid-pyridine) interactions in the amorphous state. In the current study, the molecular speciation is explored with regard to the phase transition from the amorphous to the crystalline state. Using spectroscopic techniques, the molecular interactions and structural evolvement during the recrystallization from the glassy state were investigated. The results unveiled that the structurally heterogeneous amorphous state contains acid-pyridine aggregates - either as hydrogen-bonded neutral molecules or as zwitterions - as well as a population of carboxylic acid dimers. Phase transition from the amorphous state results in crystal structures composed of carboxylic acid dimer (acid-acid) synthon or acid-pyridine chains depending on the crystallization conditions employed. The study underlines the structural evolvement, as well as its impact on the metastability, of amorphous samples from local, supramolecular assemblies to long-range intermolecular ordering through crystallization.

Chemical trapping and characterization of small oxoacids of sulfur (SOS) generated in aqueous oxidations of H2S.

PubMed

Kumar, Murugaeson R; Farmer, Patrick J

2018-04-01

Small oxoacids of sulfur (SOS) are elusive molecules like sulfenic acid, HSOH, and sulfinic acid, HS(O)OH, generated during the oxidation of hydrogen sulfide, H 2 S, in aqueous solution. Unlike their alkyl homologs, there is a little data on their generation and speciation during H 2 S oxidation. These SOS may exhibit both nucleophilic and electrophilic reactivity, which we attribute to interconversion between S(II) and S(IV) tautomers. We find that SOS may be trapped in situ by derivatization with nucleophilic and electrophilic trapping agents and then characterized by high resolution LC MS. In this report, we compare SOS formation from H 2 S oxidation by a variety of biologically relevant oxidants. These SOS appear relatively long lived in aqueous solution, and thus may be involved in the observed physiological effects of H 2 S. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2014-05-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices, including diesel particulate filters (DPFs), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOCs). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle,~Urban Dynamometer Driving Schedule, and creep + idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photooxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary PM emissions and SOA production from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after 3 h of oxidation at typical urban VOC / NOx ratios (3 : 1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the nonmethane organic gas emissions that could not be speciated using traditional one-dimensional gas chromatography. The unspeciated organics - likely comprising less volatile species such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep + idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

Sorption and speciation of selenium in boreal forest soil.

PubMed

Söderlund, Mervi; Virkanen, Juhani; Holgersson, Stellan; Lehto, Jukka

2016-11-01

Sorption and speciation of selenium in the initial chemical forms of selenite and selenate were investigated in batch experiments on humus and mineral soil samples taken from a 4-m deep boreal forest soil excavator pit on Olkiluoto Island, on the Baltic Sea coast in southwestern Finland. The HPLC-ICP-MS technique was used to monitor any possible transformations in the selenium liquid phase speciation and to determine the concentrations of selenite and selenate in the samples for calculation of the mass distribution coefficient, K d , for both species. Both SeO 3 2- and SeO 4 2- proved to be resistant forms in the prevailing soil conditions and no changes in selenium liquid phase speciation were seen in the sorption experiments in spite of variations in the initial selenium species, incubation time or conditions, pH, temperature or microbial activity. Selenite sorption on the mineral soil increased with time in aerobic conditions whilst the opposite trend was seen for the anaerobic soil samples. Selenite retention correlated with the contents of organic matter and weakly crystalline oxides of aluminum and iron, solution pH and the specific surface area. Selenate exhibited poorer sorption on soil than selenite and on average the K d values were 27-times lower. Mineral soil was more efficient in retaining selenite and selenate than humus, implicating the possible importance of weakly crystalline aluminum and iron oxides for the retention of oxyanions in Olkiluoto soil. Sterilization of the soil samples decreased the retention of selenite, thus implying some involvement of soil microbes in the sorption processes or a change in sample composition, but it produced no effect for selenate. There was no sorption of selenite by quartz, potassium feldspar, hornblende or muscovite. Biotite showed the best retentive properties for selenite in the model soil solution at about pH 8, followed by hematite, plagioclase and chlorite. The K d values for these minerals were 18, 14, 8 and 7 L/kg, respectively. It is proposed that selenite sorption is affected by the structural Fe(II) in biotite, which is capable of inducing the reduction of SeO 3 2- to Se(0). Selenite probably forms a surface complex with Fe(III) atoms on the surface of hematite, thus explaining its retention on this mineral. None of the minerals retained selenate to any extent. Copyright © 2016 Elsevier Ltd. All rights reserved.

The role of allophane nano-structure and Fe oxide speciation for hosting soil organic matter in an allophanic Andosol

NASA Astrophysics Data System (ADS)

Filimonova, Svetlana; Kaufhold, Stephan; Wagner, Friedrich E.; Häusler, Werner; Kögel-Knabner, Ingrid

2016-05-01

We evaluated the impact of nano-structural characteristics of allophanic compounds and Fe oxide speciation on the efficiency of organo-mineral interactions in an allophanic Andosol derived from volcanic ash (Eifel mountains, Germany). The samples selected for our work represented a gradient from: (i) a pure synthetic allophane and (ii) model organo-mineral mixtures to (iii) particle size fractions of the natural Andosol. We thus aimed to link the processes operating at the individual molecular scale to the phenomena active at the aggregate scale. For a non-destructive characterization of the samples, we applied 129Xe NMR spectroscopy of adsorbed Xe atoms (to identify the mineral nano-structure and surface acid centres), ESEM (verifying the nano-spherical structure of allophane), 13C CPMAS NMR (for the nature of the soil organic matter (SOM)), 57Fe Mössbauer spectroscopy (Fe oxide speciation), and N2 adsorption (contribution of micro- and mesoporosity). By using the atomic probe Xe, we obtained evidence for a coupled mechanism of adsorption onto allophane requiring both the narrow pores (voids formed by the primary nano-spherules) and the acid centres located at the defect surfaces of the primary spherules. The validity of this coupled mechanism for the sorption of organic matter was confirmed by the concomitant blocking of acid centres (129Xe NMR data) and the decrease of the N2-available pore volumes (Vmicro and Vmeso) in the model samples DOM/- and NOM/allophane (DOM = dissolved OM, NOM = natural OM). In the Andosol, the high resistance of SOM against oxidation (OCresist = 15-50%) was combined with preferential accumulation of certain organic compounds, e.g. potentially labile substrates such as carbohydrates, and the low molecular weight species such as amino acids. This feature was attributed to the peculiar microporous tortuous structure of allophane aggregates that likely impose certain criteria for the chemical nature and size of mineral-bound SOM. On the other hand, the revealed dominance of nanoparticulate Fe oxyhydroxides (57% ferrihydrite) and Fe-substituted allophane (supposedly formed due to co-precipitation of the Al, Si and Fe in the course of volcanic soil formation) may substantially contribute to the formation of highly resistant organo-mineral associations through the enhanced extent of reactive surface groups in nanoparticles, increased surface charge density and electron accepting properties of substituting Fe3+ species that supposedly enhance the proportion of oxidised organic components.

Advances in the detection of as in environmental samples using low energy X-ray fluorescence in a scanning transmission X-ray microscope: arsenic immobilization by an Fe(II)-oxidizing freshwater bacteria.

PubMed

Hitchcock, A P; Obst, M; Wang, J; Lu, Y S; Tyliszczak, T

2012-03-06

Speciation and quantitative mapping of elements, organic and inorganic compounds, and mineral phases in environmental samples at high spatial resolution is needed in many areas of geobiochemistry and environmental science. Scanning transmission X-ray microscopes (STXMs) provide a focused beam which can interrogate samples at a fine spatial scale. Quantitative chemical information can be extracted using the transmitted and energy-resolved X-ray fluorescence channels simultaneously. Here we compare the relative merits of transmission and low-energy X-ray fluorescence detection of X-ray absorption for speciation and quantitative analysis of the spatial distribution of arsenic(V) within cell-mineral aggregates formed by Acidovorax sp. strain BoFeN1, an anaerobic nitrate-reducing Fe(II)-oxidizing β-proteobacteria isolated from the sediments of Lake Constance. This species is noted to be highly tolerant to high levels of As(V). Related, As-tolerant Acidovorax-strains have been found in As-contaminated groundwater wells in Bangladesh and Cambodia wherein they might influence the mobility of As by providing sorption sites which might have different properties as compared to chemically formed Fe-minerals. In addition to demonstrating the lower detection limits that are achieved with X-ray fluorescence relative to transmission detection in STXM, this study helps to gain insights into the mechanisms of As immobilization by biogenic Fe-mineral formation and to further the understanding of As-resistance of anaerobic Fe(II)-oxidizing bacteria.

Recrystallization of Manganite (γ-MnOOH) and Implications for Trace Element Cycling.

PubMed

Hens, Tobias; Brugger, Joël; Cumberland, Susan A; Etschmann, Barbara; Frierdich, Andrew J

2018-02-06

The recrystallization of Mn(III,IV) oxides is catalyzed by aqueous Mn(II) (Mn(II) aq ) during (bio)geochemical Mn redox cycling. It is poorly understood how trace metals associated with Mn oxides (e.g., Ni) are cycled during such recrystallization. Here, we use X-ray absorption spectroscopy (XAS) to examine the speciation of Ni associated with Manganite (γ-Mn(III)OOH) suspensions in the presence or absence of Mn(II) aq under variable pH conditions (pH 5.5 and 7.5). In a second set of experiments, we used a 62 Ni isotope tracer to quantify the amount of dissolved Ni that exchanges with Ni incorporated in the Manganite crystal structure during reactions in 1 mM Mn(II) aq and in Mn(II)-free solutions. XAS spectra show that Ni is initially sorbed on the Manganite mineral surface and is progressively incorporated into the mineral structure over time (13% after 51 days) even in the absence of dissolved Mn(II). The amount of Ni incorporation significantly increases to about 40% over a period of 51 days when Mn(II) aq is present in solution. Similarly, Mn(II) aq promotes Ni exchange between Ni-substituted Manganite and dissolved Ni(II), with around 30% of Ni exchanged at pH 7.5 over the duration of the experiment. No new mineral phases are detected following recrystallization as determined by X-ray diffraction and XAS. Our results reveal that Mn(II)-catalyzed mineral recrystallization partitions Ni between Mn oxides and aqueous fluids and can therefore affect Ni speciation and mobility in the environment.

SPECIATE 4.3: Addendum to SPECIATE 4.2--Speciation database development documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

SPECIATE 4.0: SPECIATION DATABASE DEVELOPMENT DOCUMENTATION--FINAL REPORT

EPA Science Inventory

SPECIATE is the U.S. EPA's repository of total organic compounds (TOC) and particulate matter (PM) speciation profiles of air pollution sources. This report documents how EPA developed the SPECIATE 4.0 database that replaces the prior version, SPECIATE 3.2. SPECIATE 4.0 includes ...

Micro-XANES Determination Fe Speciation in Natural Basalts at Mantle-Relevant fO2

NASA Astrophysics Data System (ADS)

Fischer, R.; Cottrell, E.; Lanzirotti, A.; Kelley, K. A.

2007-12-01

We demonstrate that the oxidation state of iron (Fe3+/ΣFe) can be determined with a precision of ±0.02 (10% relative) on natural basalt glasses at mantle-relevant fO2 using Fe K-edge X-ray absorption near edge structure (XANES) spectroscopy. This is equivalent to ±0.25 log unit resolution relative to the QFM buffer. Precise determination of the oxidation state over this narrow range (Fe3+/ΣFe=0.06-0.30) and at low fO2 (down to QFM-2) relies on appropriate standards, high spectral resolution, and highly reproducible methods for extracting the pre-edge centroid position. We equilibrated natural tholeiite powder in a CO/CO2 gas mixing furnace at 1350°C from QFM-3 to QFM+2 to create six glasses of known Fe3+/ΣFe, independently determined by Mössbauer spectroscopy. XANES spectra were collected at station X26A at NSLS, Brookhaven Natl. Lab, in fluorescence mode (9 element Ge array detector) using both Si(111) and Si(311) monochromators. Generally, the energy position of the 1s→3d (pre-edge) transition centroid is the most sensitive monitor of Fe oxidation state using XANES. For the mixture of Fe oxidation states in these glasses and the resulting coordination geometries, the pre-edge spectra are best defined by two multiple 3d crystal field transitions. The Si(311) monochromator, with higher energy resolution, substantially improved spectral resolution for the 1s→3d transition. Dwell times of 5s at 0.1eV intervals across the pre-edge region yielded spectra with the 1s→3d transition peaks clearly resolved. The pre-edge centroid position is highly sensitive to the background subtraction and peak fitting procedures. Differences in fitting models result in small but significant differences in the calculated peak area of each pre-edge multiplet, and the relative contribution of each peak to the calculated centroid. We assessed several schemes and obtained robust centroid positions by simultaneously fitting the background with a damped harmonic oscillator (DHO) function and pre-edge features with two Gaussians over a sub-sample of the pre-edge region (7110-7120 eV). We found that the relation between Fe3+/ΣFe and the centroid energy is non-linear over this fO2 range, which is expected if the coordination environment changes with oxidation state. ΔQFM is linearly related (R2=0.99) to the centroid position. This new calibration allows the oxidation states of natural mantle melts to be discriminated with high spatial resolution (9μm). We apply the new calibration to determination of Fe3+/ΣFe in natural basaltic glasses and olivine-hosted glass inclusions (Cottrell et al. & Kelley et al., this meeting).

Evolution, biogeography, and systematics of Puriana: evolution and speciation in Ostracoda, III.

USGS Publications Warehouse

Cronin, T. M.

1987-01-01

Three types of geographic isolation - land barriers, deep water barriers, and climatic barriers - resulted in three distinct evolutionary responses in Neogene and Quaternary species of the epineritic ostracode genus Puriana. Through systematic, paleobiogeographic, and morphologic study of several hundred fossil and Recent populations from the eastern Pacific, western Atlantic, Gulf of Mexico, and the Caribbean, the phylogeny of the genus and the geography of speciation events were determined. Isolation of large populations by the Isthumus of Panama during the Pliocene did not lead to lineage splitting in species known to have existed before the Isthmus formed. Conversely, the establishment of small isolated populations on Caribbean islands by passive dispersal mechanisms frequently led to the evolution of new species or subspecies. Climatic changes along the southeastern United States during the Pliocene also catalyzed possible parapatric speciation as populations that immigrated to the northeastern periphery of the genus' range split to form new species. The results provide evidence that evolutionary models describing the influence of abiotic events on patterns of evolution and speciation can be tested using properly selected tectonic and climatic events and fossil groups amenable to species-level analysis. Two new species, P. bajaensis and P. paikensis, are described. -Author

Plasma Assisted Combustion: Flame Regimes and Kinetic Studies

DTIC Science & Technology

2015-01-05

Kinetic model Fuel: Dimethyl ether Oxidizer= (1-x)O2 + xO3, x=0 - 0.1, p=1 atm Ozone chemistry & Dimethyl ether model ...diffusional cool flames • A heated counterflow burner integrated with vaporization system1 • n-heptane/nitrogen vs. oxygen/ ozone • Ozone generator...micro-DBD) produces 2- 5 % of ozone in oxygen stream, depending on oxygen flow rate • Speciation profiles by using a micro-probe sampling with a

The effects of metamorphism on iron mineralogy and the iron speciation redox proxy

NASA Astrophysics Data System (ADS)

Slotznick, Sarah P.; Eiler, John M.; Fischer, Woodward W.

2018-03-01

As the most abundant transition metal in the Earth's crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite's identification depended on the extraction techniques utilized. The presence of diagenetic iron carbonates in many samples severely affected the proxy even at low grade, engendering an interpretation of ferruginous conditions in all lithologies, but particularly in carbonate-bearing rocks. Increasing metamorphic grades transformed iron in carbonates into iron in silicate minerals, which when combined with a slight increase in the amount of pyrrhotite, drove the proxy toward more oxic and more euxinic conditions. Broad-classes of metamorphic reactions (e.g. decarbonation, silicate formation) occurred at distinct temperatures-pressures in carbonates versus siliciclastics, and could be either abrupt between metamorphic facies or more gradual in nature. Notably, these analyses highlighted the importance of trace iron in phases like calcite, which otherwise might not be included in iron-focused research i.e. ore-system petrogenesis, metamorphic evolution, or normative calculations of mineral abundance. The observations show that iron is mobile and reactive during diagenesis and metamorphism, and these post-depositional processes can readily overprint primary redox information held by iron speciation. However, in principle, additional mineralogical and petrographic approaches can be combined with iron speciation data to help untangle many of these post-depositional processes and arrive at more accurate estimates of paleoenvironmental redox conditions and processes, even for metamorphosed samples.

Diel Variability of Total and Speciated Water-Soluble Inorganic Iodine in PM2.5 Aerosol at a Southern California Coastal Site

NASA Astrophysics Data System (ADS)

Pszenny, A.; Cotter, K.; Deegan, B.; Fischer, E.; Johnson, D.

2007-12-01

PM2.5 aerosol was sampled over nominal 3-hour intervals at the head of Zuma Beach in Malibu, California (USA) from 6 to 24 October 2006 by filtration at 1.13 m3 min-1 (STP) through 20 x 25 cm cellulose fiber (Whatman 41) filters that had been rinsed with deionized water (DIW). Exposed filters were removed from support cartridges as soon as possible after retrieval (usually within 2 hours), immediately sealed in clean polyethylene bags, and stored frozen until further processing. Following the field campaign one quarter of each filter was pressed into a pellet (2.0 cm diameter x 0.5 cm thick) and analyzed by neutron activation for total concentrations of I and several other trace elements. Our preliminary analyses indicate that sodium and iodine show a clear diel variation characterized by higher concentrations from late morning to early evening. We hypothesize that this diel variability is related to a persistent land/sea breeze circulation associated with the nearby coastal region. Other elements are indicative of variability in other aerosol sources such as soil dust (Al, Mn) and fossil fuel combustion (V). Second quarters are currently being extracted in DIW and analyzed in two ways: 1) for iodide by ion chromatography, and 2) for inorganic iodine in higher oxidation states (i.e., V to 0) by chemical reduction with ascorbic acid followed by determination of iodide by ion chromatography. Results of the trace element and speciated iodine analyses will be presented.

[Determination of cadmium by HG-aFS in soil of virescent zone in Chengdu city].

PubMed

Chen, Yuan; Zeng, Ying; Wu, Hong-ji; Wang, Qin-er

2008-12-01

The different speciations of cadmium in soil samples from Chengdu greenbelt were extracted by Tessier sequential extraction method. The contents of total cadmium and different speciation cadmium were determined using HG-AFS. Under optimization condition of HG-AFS and using 2% HCl as medium, and 30 g x L(-1) KBH4 as reductive reagent, 1 mg x L(-1) Co2+ acting together with 10 g x L(-1) CH4N2S can advance the generating efficiency of cadmium compound. The effects of the coexisting elements in soil on the determination of cadmium can be reduced if certain amount of Na4P2O7, K2SO4 and BaCl2 are added. The linear range is 0-10 mg x L(-1) with r=0.9991 and the detection limit is 0.016 mg x L(-1). The recovery is 97.80%-100.2% with RSD of 1.93%. The analytical method is very sensitive and accurate. The distribution of average percentage of five speciations of cadmium in experimental soil samples is: residual fraction (62.1%) > exchangeable fraction (11.7%) > Fe-Mn oxide-bound (9.71%) > carbonate-bound (4.17%) > organic-bound (3.47%). Although residual fraction is the main speciation of cadmium in soil, the content of exchangeable fraction is relatively high. Thus the bioactivity of cadmium in the research area should be recognized. The concentration of cadmium exceeds the country standard in 19 soil sample, accounting for 86. 4% of all soil samples. The soil from Chengdu greenbelt located in 1st ring road, 2nd ring road and 3rd ring road was polluted to different degree. The relative pollution magnitude of them is: 2nd ring road > 1st ring road > 3rd ring road.

[Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

PubMed

Shen, Ya-Ting

2014-03-01

In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability.

Speciation Analysis of Arsenic by Selective Hydride Generation-Cryotrapping-Atomic Fluorescence Spectrometry with Flame-in-Gas-Shield Atomizer: Achieving Extremely Low Detection Limits with Inexpensive Instrumentation

PubMed Central

2015-01-01

This work describes the method of a selective hydride generation-cryotrapping (HG-CT) coupled to an extremely sensitive but simple in-house assembled and designed atomic fluorescence spectrometry (AFS) instrument for determination of toxicologically important As species. Here, an advanced flame-in-gas-shield atomizer (FIGS) was interfaced to HG-CT and its performance was compared to a standard miniature diffusion flame (MDF) atomizer. A significant improvement both in sensitivity and baseline noise was found that was reflected in improved (4 times) limits of detection (LODs). The yielded LODs with the FIGS atomizer were 0.44, 0.74, 0.15, 0.17 and 0.67 ng L–1 for arsenite, total inorganic, mono-, dimethylated As and trimethylarsine oxide, respectively. Moreover, the sensitivities with FIGS and MDF were equal for all As species, allowing for the possibility of single species standardization with arsenate standard for accurate quantification of all other As species. The accuracy of HG-CT-AFS with FIGS was verified by speciation analysis in two samples of bottled drinking water and certified reference materials, NRC CASS-5 (nearshore seawater) and SLRS-5 (river water) that contain traces of methylated As species. As speciation was in agreement with results previously reported and sums of all quantified species corresponded with the certified total As. The feasibility of HG-CT-AFS with FIGS was also demonstrated by the speciation analysis in microsamples of exfoliated bladder epithelial cells isolated from human urine. The results for the sums of trivalent and pentavalent As species corresponded well with the reference results obtained by HG-CT-ICPMS (inductively coupled plasma mass spectrometry). PMID:25300934

Responses of Mn2+ speciation in Deinococcus radiodurans and Escherichia coli to γ-radiation by advanced paramagnetic resonance methods

PubMed Central

Sharma, Ajay; Gaidamakova, Elena K.; Matrosova, Vera Y.; Bennett, Brian; Daly, Michael J.; Hoffman, Brian M.

2013-01-01

The remarkable ability of bacterium Deinococcus radiodurans to survive extreme doses of γ-rays (12,000 Gy), 20 times greater than Escherichia coli, is undiminished by loss of Mn-dependent superoxide dismutase (SodA). D. radiodurans radiation resistance is attributed to the accumulation of low-molecular-weight (LMW) “antioxidant” Mn2+–metabolite complexes that protect essential enzymes from oxidative damage. However, in vivo information about such complexes within D. radiodurans cells is lacking, and the idea that they can supplant reactive-oxygen-species (ROS)–scavenging enzymes remains controversial. In this report, measurements by advanced paramagnetic resonance techniques [electron-spin-echo (ESE)-EPR/electron nuclear double resonance/ESE envelope modulation (ESEEM)] reveal differential details of the in vivo Mn2+ speciation in D. radiodurans and E. coli cells and their responses to 10 kGy γ-irradiation. The Mn2+ of D. radiodurans exists predominantly as LMW complexes with nitrogenous metabolites and orthophosphate, with negligible EPR signal from Mn2+ of SodA. Thus, the extreme radiation resistance of D. radiodurans cells cannot be attributed to SodA. Correspondingly, 10 kGy irradiation causes no change in D. radiodurans Mn2+ speciation, despite the paucity of holo-SodA. In contrast, the EPR signal of E. coli is dominated by signals from low-symmetry enzyme sites such as that of SodA, with a minority pool of LMW Mn2+ complexes that show negligible coordination by nitrogenous metabolites. Nonetheless, irradiation of E. coli majorly changes LMW Mn2+ speciation, with extensive binding of nitrogenous ligands created by irradiation. We infer that E. coli is highly susceptible to radiation-induced ROS because it lacks an adequate supply of LMW Mn antioxidants. PMID:23536297

Estimation of speciated and total mercury dry deposition at monitoring locations in eastern and central North America

USGS Publications Warehouse

Zhang, L.; Blanchard, P.; Gay, D.A.; Prestbo, E.M.; Risch, M.R.; Johnson, D.; Narayan, J.; Zsolway, R.; Holsen, T.M.; Miller, E.K.; Castro, M.S.; Graydon, J.A.; St. Louis, V.L.; Dalziel, J.

2012-01-01

Dry deposition of speciated mercury, i.e., gaseous oxidized mercury (GOM), particulate-bound mercury (PBM), and gaseous elemental mercury (GEM), was estimated for the year 2008–2009 at 19 monitoring locations in eastern and central North America. Dry deposition estimates were obtained by combining monitored two- to four-hourly speciated ambient concentrations with modeled hourly dry deposition velocities (Vd) calculated using forecasted meteorology. Annual dry deposition of GOM+PBM was estimated to be in the range of 0.4 to 8.1 μg m−2 at these locations with GOM deposition being mostly five to ten times higher than PBM deposition, due to their different modeled Vd values. Net annual GEM dry deposition was estimated to be in the range of 5 to 26 μg m−2 at 18 sites and 33 μg m−2 at one site. The estimated dry deposition agrees very well with limited surrogate-surface dry deposition measurements of GOM and PBM, and also agrees with litterfall mercury measurements conducted at multiple locations in eastern and central North America. This study suggests that GEM contributes much more than GOM+PBM to the total dry deposition at the majority of the sites considered here; the only exception is at locations close to significant point sources where GEM and GOM+PBM contribute equally to the total dry deposition. The relative magnitude of the speciated dry deposition and their good comparisons with litterfall deposition suggest that mercury in litterfall originates primarily from GEM, which is consistent with the limited number of previous field studies. The study also supports previous analyses suggesting that total dry deposition of mercury is equal to, if not more important than, wet deposition of mercury on a regional scale in eastern North America.

Metal speciation in landfill leachates with a focus on the influence of organic matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Claret, Francis, E-mail: f.claret@brgm.fr; Tournassat, Christophe; Crouzet, Catherine

Highlights: > This study characterises the heavy-metal content in leachates collected from eight landfills in France. > Most of the metals are concentrated in the <30 kDa fraction, while Pb, Cu and Cd are associated with larger particles. > Metal complexation with OM is not sufficient to explain apparent supersaturation of metals with sulphide minerals. - Abstract: This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmospheremore » to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Speciation analysis of arsenic by selective hydride generation-cryotrapping-atomic fluorescence spectrometry with flame-in-gas-shield atomizer: achieving extremely low detection limits with inexpensive instrumentation.

PubMed

Musil, Stanislav; Matoušek, Tomáš; Currier, Jenna M; Stýblo, Miroslav; Dědina, Jiří

2014-10-21

This work describes the method of a selective hydride generation-cryotrapping (HG-CT) coupled to an extremely sensitive but simple in-house assembled and designed atomic fluorescence spectrometry (AFS) instrument for determination of toxicologically important As species. Here, an advanced flame-in-gas-shield atomizer (FIGS) was interfaced to HG-CT and its performance was compared to a standard miniature diffusion flame (MDF) atomizer. A significant improvement both in sensitivity and baseline noise was found that was reflected in improved (4 times) limits of detection (LODs). The yielded LODs with the FIGS atomizer were 0.44, 0.74, 0.15, 0.17 and 0.67 ng L(-1) for arsenite, total inorganic, mono-, dimethylated As and trimethylarsine oxide, respectively. Moreover, the sensitivities with FIGS and MDF were equal for all As species, allowing for the possibility of single species standardization with arsenate standard for accurate quantification of all other As species. The accuracy of HG-CT-AFS with FIGS was verified by speciation analysis in two samples of bottled drinking water and certified reference materials, NRC CASS-5 (nearshore seawater) and SLRS-5 (river water) that contain traces of methylated As species. As speciation was in agreement with results previously reported and sums of all quantified species corresponded with the certified total As. The feasibility of HG-CT-AFS with FIGS was also demonstrated by the speciation analysis in microsamples of exfoliated bladder epithelial cells isolated from human urine. The results for the sums of trivalent and pentavalent As species corresponded well with the reference results obtained by HG-CT-ICPMS (inductively coupled plasma mass spectrometry).

Identification of Antimony- and Arsenic-Oxidizing Bacteria Associated with Antimony Mine Tailing

PubMed Central

Hamamura, Natsuko; Fukushima, Koh; Itai, Takaaki

2013-01-01

Antimony (Sb) is a naturally occurring toxic element commonly associated with arsenic (As) in the environment and both elements have similar chemistry and toxicity. Increasing numbers of studies have focused on microbial As transformations, while microbial Sb interactions are still not well understood. To gain insight into microbial roles in the geochemical cycling of Sb and As, soils from Sb mine tailing were examined for the presence of Sb- and As-oxidizing bacteria. After aerobic enrichment culturing with AsIII (10 mM) or SbIII (100 μM), pure cultures of Pseudomonas- and Stenotrophomonas-related isolates with SbIII oxidation activities and a Sinorhizobium-related isolate capable of AsIII oxidation were obtained. The AsIII-oxidizing Sinorhizobium isolate possessed the aerobic arsenite oxidase gene (aioA), the expression of which was induced in the presence of AsIII or SbIII. However, no SbIII oxidation activity was detected from the Sinorhizobium-related isolate, suggesting the involvement of different mechanisms for Sb and As oxidation. These results demonstrate that indigenous microorganisms associated with Sb mine soils are capable of Sb and As oxidation, and potentially contribute to the speciation and mobility of Sb and As in situ. PMID:23666539

Treatment of municipal sewage sludge in supercritical water: A review.

PubMed

Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Laisheng

2016-02-01

With increasing construction of wastewater treatment plants and stricter policies, municipal sewage sludge (MSS) disposal has become a serious problem. Treatment of MSS in supercritical water (SCW) can avoid the pre-drying procedure and secondary pollution of conventional methods. SCW treatment methods can be divided into supercritical water gasification (SCWG), supercritical water partial oxidation (SCWPO) and supercritical water oxidation (SCWO) technologies with increasing amounts of oxidants. Hydrogen-rich gases can be generated from MSS by SCWG or SCWPO technology using oxidants less than stoichiometric ratio while organic compounds can be completely degraded by SCWO technology with using an oxidant excess. For SCWG and SCWPO technologies, this paper reviews the influences of different process variables (MSS properties, moisture content, temperature, oxidant amount and catalysts) on the production of gases. For SCWO technology, this paper reviews research regarding the removal of organics with or without hydrothermal flames and the changes in heavy metal speciation and risk. Finally, typical systems for handling MSS are summarized and research needs and challenges are proposed. Copyright © 2015 Elsevier Ltd. All rights reserved.

XANES study of elemental mercury oxidation over RuO 2/TiO 2 and selective catalytic reduction catalysts for mercury emissions control

DOE PAGES

Liu, Zhouyang; Li, Can; Sriram, Vishnu; ...

2016-07-25

Linear combination fitting of the X-ray Absorption Near Edge Spectroscopy (XANES) was used to quantify oxidized mercury species over RuO 2/TiO 2 and Selective Catalytic Reduction (SCR) catalysts under different simulated flue gas conditions. Halogen gases play a major role in mercury oxidation. In the absence of halogen gas, elemental mercury can react with sulfur that is contained in both the RuO2/TiO2 and SCR catalysts to form HgS and HgSO 4. In the presence of HCl or HBr gas, HgCl 2 or HgBr 2 is the main oxidized mercury species. When both HCl and HBr gases are present, HgBr2 ismore » the preferred oxidation product and no HgCl 2 can be found. The formation of HgO and HgS cannot be neglected with or without halogen gas. Other simulated flue gas components such as NO, NH 3, SO 2 and CO 2 do not have significant effect on oxidized mercury speciation when halogen gas is present.« less

Source-receptor reconciliation of fine-particulate emissions from residential wood combustion in the southeastern United States

EPA Science Inventory

An extensive collection of speciated PM2.5 measurements including organic tracers permitted a detailed examination of the emissions from residential wood combustion (RWC) in the southeastern United States over an entire year (2007). The Community Multiscale Air Quality model-base...

General trends of atmospheric mercury concentrations in urban and rural areas in Korea and characteristics of high-concentration events

NASA Astrophysics Data System (ADS)

Han, Young-Ji; Kim, Jung-Eun; Kim, Pyung-Rae; Kim, Woo-Jin; Yi, Seung-Muk; Seo, Yong-Seok; Kim, Seung-Hee

2014-09-01

Long-term measurement of speciated Hg concentrations is the first step toward identifying the seasonal and spatial characteristics of Hg concentrations; however, atmospheric Hg research is scarce in Korea. In this study, total gaseous mercury (TGM), gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) were measured in urban (Seoul) and rural (Chuncheon) areas over a more than 3 year period in order to improve the understanding of speciated Hg transport. The mean concentrations of TGM, GOM and PBM were 3.72 ± 2.96 (0.19-149.84) ng m-3, 11.3 ± 9.5 (0.9-57.3) pg m-3, and 13.4 ± 12.0 (2.1-64.3) pg m-3 at the Seoul site and 2.12 ± 1.47 (0.26-10.75) ng m-3, 2.7 ± 2.7 (0.1-16.9) pg m-3, and 3.7 ± 5.7 (0.1-30.0) pg m-3 in Chuncheon. Both long-range transport and local sources caused high TGM concentration events, while local coal combustion was a main cause of enhancing the GOM and PBM concentrations in Seoul. However, there was no correlation between the pollutants emitted from coal combustion and the speciated Hg concentration in Chuncheon, indicating that other mechanisms were involved in the Hg increase. We found a positive correlation between the GOM and the O3 concentrations and a negative correlation between the GEM and the GOM concentrations, especially on foggy days, suggesting that the oxidation of GEM was an important source for GOM in Chuncheon. In addition, the ratio of PBM/GOM was inversely proportional to the atmospheric temperature and directly proportional to the relative humidity, which suggests that the in-situ formation of PBM through gas-particle partitioning of GOM was important in rural areas.

Understanding atmospheric mercury speciation and mercury in snow over time at Alert, Canada

NASA Astrophysics Data System (ADS)

Steffen, A.; Bottenheim, J.; Cole, A.; Ebinghaus, R.; Lawson, G.; Leaitch, W. R.

2013-06-01

Ten years of atmospheric mercury speciation data and 14 yr of mercury in snow data from Alert, Nunavut, Canada are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentrations of PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pg m-3 and RGM is 23.9 pg m-3 from March to June in comparison to the annual median concentrations of 11.3 and 3.2 -3 for PHg and RGM, respectively. In each of the ten years of sampling, PHg increases steadily from January through March and is higher than RGM. This pattern begins to change in April with very high levels of PHg and increasing RGM. In May, RGM transitions to be significantly higher than PHg and continues into June whereas PHg sharply drops down. The transition is thought to be driven by a combination of air temperature and particle availability. Firstly, the ratio of PHg to RGM is favoured by low temperatures suggesting that oxidized mercury may partition to available particles to form PHg. Prior to the transition, the median air temperature is -24.8 °C and after the transition the median air temperature is -5.8 °C. Secondly, high aerosol levels in the spring are a strong driver for the high PHg concentrations. In February through April, partitioning of oxidized mercury to produce PHg was favoured by increased concentrations of particles that are principally the result of Arctic Haze and some sea salts. In the snow, the concentrations of mercury peak in May for all years. The highest deposition of mercury to the snow in the spring at Alert is during and after the transition of PHg to RGM in the atmosphere.

Impact of Fe(III)-OM complexes and Fe(III) polymerization on SOM pools reactivity under different land uses

NASA Astrophysics Data System (ADS)

Giannetta, B.; Plaza, C.; Zaccone, C.; Siebecker, M. G.; Rovira, P.; Vischetti, C.; Sparks, D. L.

2017-12-01

Soil organic matter (SOM) protection and long-term accumulation are controlled by adsorption to mineral surfaces in different ways, depending on its molecular structure and pedo-climatic conditions. Iron (Fe) oxides are known to be key regulators of the soil carbon (C) cycle, and Fe speciation in soils is highly dependent on environmental conditions and chemical interactions with SOM. However, the molecular structure and hydrolysis of Fe species formed in association with SOM is still poorly described. We hypothesize the existence of two pools of Fe which interact with SOM: mononuclear Fe(III)-SOM complexes and precipitated Fe(III) hydroxides. To verify our hypothesis, we investigated the interactions between Fe(III) and physically isolated soil fractions by means of batch experiments at pH 7. Specifically, we examined the fine silt plus clay (FSi+C) fraction, obtained by ultrasonic dispersion and wet sieving. The soil samples spanned several land uses, including coniferous forest (CFS), grassland (GS), technosols (TS) and agricultural (AS) soils. Solid phase products and supernatants were analyzed for C and Fe content. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis were also performed. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was used to assess the main C functional groups involved in C complexation and desorption experiments. Preliminary linear combination fitting (LCF) of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra suggested the formation of ferrihydrite-like polymeric Fe(III) oxides in reacted CFS and GS samples, with higher C and Fe concentration. Conversely, mononuclear Fe(III) OM complexes dominated the speciation for TS and AS samples, characterized by lower C and Fe concentration, inhibiting the hydrolysis and polymerization of Fe (III). This approach will help revealing the mechanisms by which SOM pools can control Fe(III) speciation, and will elucidate how both Fe(III)-OM complexes and Fe(III) polymerization can affect SOM reactivity and, consequently, its mean residence time in different ecosystems.

Graphene oxide-TiO2 composite solid phase extraction combined with graphite furnace atomic absorption spectrometry for the speciation of inorganic selenium in water samples.

PubMed

Zhang, Yanan; Chen, Beibei; Wu, Shaowei; He, Man; Hu, Bin

2016-07-01

In this paper, a method of graphene oxide (GO)-TiO2 composite solid phase extraction followed by graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the speciation of inorganic selenium in environmental waters. The adsorption behavior of inorganic Se(IV) and Se(VI) on the GO-TiO2(1:1) composite was investigated. It was found that Se(IV) was quantitatively retained on the GO-TiO2 composites within a wide pH range of 0.5-10, while Se(VI) was quantitatively adsorbed on GO-TiO2(1:1) composite at pH 0.5-2, and no obvious adsorption of Se(VI) within the pH range of 4-10 was found. By selecting pH 6.0, Se(IV) could be easily determined. After reduction of Se(VI), total Se was determined by the proposed method, and Se(VI) was calculated as the difference between the total Se and Se(IV). The factors affecting the separation/preconcentration of Se(IV) and Se(VI) were studied. Under the optimum conditions, the isothermal adsorption of Se(IV) on the GO-TiO2(1:1) composite fitted Langmuir model; a linear range over 0.1-12ngmL(-1) was obtained. The limit of detection (LOD) and precision of the method for Se(IV) was 0.04ngmL(-1) and 9.4% (cSe(IV)=0.5ngmL(-1), n=7), respectively. In order to verify the accuracy of the method, a standard water sample (GSBZ50031-94) was analyzed, and the determined value was in a good agreement to the certified value. The established method was applied to inorganic Se speciation in environmental water samples and the recovery of 87.4-102% was obtained for the spiked samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic.

PubMed

ThomasArrigo, Laurel K; Mikutta, Christian; Lohmayer, Regina; Planer-Friedrich, Britta; Kretzschmar, Ruben

2016-04-05

Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.

Mercury Emission Measurement in Coal-Fired Boilers by Continuous Mercury Monitor and Ontario Hydro Method

NASA Astrophysics Data System (ADS)

Zhu, Yanqun; Zhou, Jinsong; He, Sheng; Cai, Xiaoshu; Hu, Changxin; Zheng, Jianming; Zhang, Le; Luo, Zhongyang; Cen, Kefa

2007-06-01

The mercury emission control approach attaches more importance. The accurate measurement of mercury speciation is a first step. Because OH method (accepted method) can't provide the real-time data and 2-week time for results attained, it's high time to seek on line mercury continuous emission monitors(Hg-CEM). Firstly, the gaseous elemental and oxidized mercury were conducted to measure using OH and CEM method under normal operation conditions of PC boiler after ESP, the results between two methods show good consistency. Secondly, through ESP, gaseous oxidized mercury decrease a little and particulate mercury reduce a little bit, but the elemental mercury is just the opposite. Besides, the WFGD system achieved to gaseous oxidized mercury removal of 53.4%, gaseous overall mercury and elemental mercury are 37.1% and 22.1%, respectively.

Characterization of Arsenic Contamination on Rust from Ton Containers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gary S. Groenewold; Recep Avci; Robert V. Fox

The speciation and spatial distribution of arsenic on rusted steel surfaces affects both measurement and removal approaches. The chemistry of arsenic residing in the rust of ton containers that held the chemical warfare agents bis(2-chloroethyl)sulfide (sulfur mustard) and 2-chlorovinyldichloroarsine (Lewisite) is of particular interest, because while the agents have been decontaminated, residual arsenic could pose a health or environmental risk. The chemistry and distribution of arsenic in rust samples was probed using imaging secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX). Arsenic in the +3 and or +5more » oxidation state is homogeneously distributed at the very top-most layer of the rust samples, and is intimately associated with iron. Sputter depth profiling followed by SIMS and XPS shows As at a depth of several nm, in some cases in a reduced form. The SEM/EDX experiments show that As is present at a depth of several microns, but is inhomogeneously distributed; most locations contained oxidized As at concentrations of a few percent, however several locations showed very high As in a metallic form. These results indicate that the rust material must be removed if the steel containers are to be cleared of arsenic.« less

SPECIATE and using the Speciation Tool to prepare VOC and PM chemical speciation profiles for air quality modeling

EPA Science Inventory

This product provides training to air pollution inventory and modeling professionals to understand the US EPA's SPECIATE database base and Speciation Tool and their use to develop speciated emission inventories.

SPECIATE's VOC and PM Speciation Profiles and Their use to Prepare for Air quality Modeling (2017 EIC)

EPA Pesticide Factsheets

This training provides general concepts on chemical speciation, the SPECIATE database and browser, and how to use the Speciation Tool to create model ready speciation inputs for a photochemical air quality model.

SPECIATE 4.2: speciation Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

A Novel Permeable Reactive Barrier (PRB) for Simultaneous and Rapid Removal of Heavy Metal and Organic Matter - A Systematic Chemical Speciation Approach on Sustainable Technique for Pallikarani Marshland Remediation

NASA Astrophysics Data System (ADS)

Selvaraj, A.; Nambi, I. M.

2014-12-01

In this study, an innovative technique of ZVI mediated 'coupling of Fenton like oxidation of phenol and Cr(VI) reduction technique' was attempted. The hypothesis is that Fe3+ generated from Cr(VI) reduction process acts as electron acceptor and catalyst for Fenton's Phenol oxidation process. The Fe2+ formed from Fenton reactions can be reused for Cr(VI) reduction. Thus iron can be made to recycle between two reactions, changing back and forth between Fe2+ and Fe3+ forms, makes treatment sustainable.(Fig 1) This approach advances current Fenton like oxidation process by (i)single system removal of heavy metal and organic matter (ii)recycling of iron species; hence no additional iron required (iii)more contaminant removal to ZVI ratio (iv)eliminating sludge related issues. Preliminary batch studies were conducted at different modes i) concurrent removal ii) sequential removal. The sequential removal was found better for in-situ PRB applications. PRB was designed based on kinetic rate slope and half-life time, obtained from primary column study. This PRB has two segments (i)ZVI segment[Cr(VI)] (ii)iron species segment[phenol]. This makes treatment sustainable by (i) having no iron ions in outlet stream (ii)meeting hypothesis and elongates the life span of PRB. Sequential removal of contaminates were tested in pilot scale PRB(Fig 2) and its life span was calculated based on the exhaustion of filling material. Aqueous, sand and iron aliquots were collected at various segments of PRB and analyzed for precipitation and chemical speciation thoroughly (UV spectrometer, XRD, FTIR, electron microscope). Chemical speciation profile eliminates the uncertainties over in-situ PRB's long term performance. Based on the pilot scale PRB study, 'field level PRB wall construction' was suggested to remove heavy metal and organic compounds from Pallikaranai marshland(Fig 3)., which is contaminated with leachate coming from nearby Perungudi dumpsite. This research provides (i)deeper insight into the environmental friendly, accelerated, sustainable technique for combined removal of organic matter and heavy metal (ii)evaluation of the novel technique in PRB, which resulted in PRB's increased life span (iii)designing of PRB to remediate the marshland and its ecosystem, thus save the habitats related to it.

Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite weathering at historic mine sites Špania Dolina-Piesky and Lubietová-Svätodušná, Slovakia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bor,; #269; inová rAdková, AnežkA

The legacy of copper (Cu) mining at Špania Dolina-Piesky and Lubietová-Svätodušná (central Slovakia) is waste rock and soil, surface waters, and groundwaters contaminated with antimony (Sb), arsenic (As), Cu, and other metals. Copper ore is hosted in chalcopyrite (CuFeS2) and sulfosalt solid-solution tetrahedrite-tennantite {Cu6[Cu4(Fe,Zn)2]Sb4S13–Cu6[Cu4(Fe,Zn)2]As4S13} that show wide-spread oxidation characteristic by olive-green color secondary minerals. Tetrahedrite-tennantite can be a significant source of As and Sb contamination. Synchrotron-based μ-XRD, μ-XRF, and μ-XANES combined with electron microprobe analyses have been used to determine the mineralogy, chemical composition, element distribution, and Sb speciation in tetrahedrite-tennantite oxidation products in waste rock. Our results show thatmore » the mobility of Sb is limited by the formation of oxidation products such as tripuhyite and roméite group mineral containing 36.54 wt% Sb for samples where the primary mineral chemical composition is close to tetrahedrite end-member. Antimony K-edge μ-XANES spectra of these oxidation products indicate that the predominant Sb oxidation state is 5+. Arsenic and Cu are also hosted by amorphous phases containing 6.23 wt% Sb on average and these are intergrown with tripuhyite and roméite. Antimony in this environment is not very mobile, meaning it is not easily released from solid phases to water, especially compared to As, Cu, and S. For samples where the primary sulfosalt is close to tennantite composition, the oxidation products associated with tennantite relicts contain 2.43 wt% Sb and are amorphous. The variable solubility of the secondary minerals that have been identified is expected to influence mobility of Sb and As in near-surface environment.« less

Antimicrobial Tolerance in Biofilms

PubMed Central

Stewart, Philip S.

2015-01-01

The tolerance of microorganisms in biofilms to antimicrobial agents is examined through a meta-analysis of literature data. A numerical tolerance factor comparing the rates of killing in the planktonic and biofilm states is defined to provide a quantitative basis for the analysis. Tolerance factors for biocides and antibiotics range over three orders of magnitude. This variation is not explained by taking into account the molecular weight of the agent, the chemistry of the agent, the substratum material, or the speciation of the microorganisms. Tolerance factors do depend on the areal cell density of the biofilm at the time of treatment and on the age of the biofilm as grown in a particular experimental system. This suggests that there is something that happens during biofilm maturation, either physical or physiological, that is essential for full biofilm tolerance. Experimental measurements of antimicrobial penetration times in biofilms range over orders of magnitude, with slower penetration (>12 min) observed for reactive oxidants and cationic molecules. These agents are retarded through the interaction of reaction, sorption, and diffusion. The specific physiological status of microbial cells in a biofilm contributes to antimicrobial tolerance. A conceptual framework for categorizing physiological cell states is discussed in the context of antimicrobial susceptibility. It is likely that biofilms harbor cells in multiple states simultaneously (e.g., growing, stress-adapted, dormant, inactive) and that this physiological heterogeneity is an important factor in the tolerance of the biofilm state. PMID:26185072

Impact on the Fe redox cycling of organic ligands released by Synechococcus PCC 7002, under different iron fertilization scenarios. Modeling approach

NASA Astrophysics Data System (ADS)

Samperio-Ramos, Guillermo; González-Dávila, Melchor; Santana-Casiano, J. Magdalena

2018-06-01

The kinetics of Fe redox transformations are of crucial importance in determining the bioavailability of iron, due to inorganic Fe(II) and Fe weakly organic complexes being the most easily assimilated species by phytoplankton. The role played by the natural organic ligands excreted by the cyanobacteria Synecococcus PCC 7002 on the iron redox chemistry was studied at different stages of growth, considering changes in the organic exudation of the cyanobacteria, associated with growth under two different scenarios of iron availability. The oxidation/reduction processes of iron were studied at nanomolar levels and under different physicochemical conditions of pH (7.2- 8.2), temperature (5- 35 °C) and salinity (10- 37). The presence of natural organic exudates of Synechococcus affected the redox behavior of iron. A pH-dependent and photo-induced Fe(III) reduction process was detected in the presence of exudates produced under Fe-Low conditions. Photolytic reactions also modified the reactivity of those exudates with respect to Fe(II), increasing its lifetime in seawater. Without light mediated processes, organic ligands excreted under iron deficient conditions intensified the Fe(II) oxidation at pH < 7.5. The organic exudates released under High-Fe conditions retarded the Fe(II) oxidation rate, as a function of DOC produced. The changes in the apparent oxidation rate were fitted to polynomial functions for both of the Fe-scenarios considered. A kinetic modeling approach to describe the speciation and the contribution of individual Fe(II) species to the overall oxidation rate was applied, considering the experimental data and delimiting the equilibrium and redox constants between iron and the major ligands present in solution. Two organic type ligands for the exudates of Synechococcus PCC 7002, with different iron-chelation properties were included in the model. The Fe(II) speciation was radically affected when organic ligands were considered. The individual contributions to the overall Fe(II) oxidation rate demonstrated that these organic ligands played a key role in the oxidation process, although their contributions were dependent on the prescribed iron conditions. The study, therefore, suggests that the variability in the composition and nature of organic exudates released, due to iron availability conditions, might determine the redox behaviour of iron in seawater.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldstein, A. H.; Yee, L. D.; Issacman-VanWertz, G.

In areas where biogenic emissions are oxidized in the presence of anthropogenic pollutants such as SO2, NOx, and black carbon, it has become increasingly apparent that secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (VOCs) is substantially enhanced. Research is urgently needed to elucidate fundamental processes of natural and anthropogenically influenced VOC oxidation and the contribution of these processes to SOA formation. GoAmazon 2014/15 afforded study of the chemical transformations in the region downwind of Manaus, Brazil, where local biogenic VOC emissions are high, and their chemical oxidation can be studied both inside and outside of the urbanmore » plume to differentiate the role of anthropogenic influence on secondary aerosol formation during oxidation of these natural VOC emissions. To understand the connection between primary biogenic VOC emissions and their secondary products that form aerosols, we made time-resolved molecular level measurements by deploying a Semi-Volatile Thermal Desorption Aerosol Gas Chromatograph (SV-TAG) and a sequential filter sampler during two intensive operational periods (IOPs) of the GoAmazon 2014/15 field campaign. The SV-TAG measured semi-volatile organic compounds in both the gas and particle phases and the sequential filter sampler collected aerosols on quartz fiber filters in four-hour increments used for offline analysis. SV-TAG employed novel online derivatization that provided chemical speciation of highly oxygenated or functionalized compounds that comprise a substantial fraction of secondary organic aerosols, yet are poorly characterized. It also provided partitioning of these compounds between the vapor and particle phases at sufficient time resolution to define the importance of competing atmospheric processes. These measurements were supported by offline analysis of the filters using two-dimensional gas chromatography (GC x GC) with high-resolution time-of-flight mass spectrometry (HR-TOF-MS) using both electron impact (EI) and soft vacuum ultraviolet (VUV) ionization with derivatization. Speciated chemical data from SV-TAG and filter measurements were used to elucidate the relative importance of potential oxidation pathways by providing detailed information on the product distribution from atmospheric reactions and the quantification of known tracers for various oxidation pathways. Together, these techniques provided unequivocal molecular identification of a wide range of atmospheric organic compounds spanning the volatile, semi-volatile, and non-volatile phases. This level of chemical characterization provided insight into the chemical and physical processes that control the atmospheric oxidation of biogenic VOC and subsequent formation of SOA.« less

Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction.

PubMed

Cruz-Hernández, Yusniel; Ruiz-García, Mismel; Villalobos, Mario; Romero, Francisco Martin; Meza-Figueroa, Diana; Garrido, Fernando; Hernández-Alvarez, Elizabeth; Pi-Puig, Teresa

2018-06-01

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values. The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry. Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides). Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found. Copyright © 2018 Elsevier Ltd. All rights reserved.

Fate and Transport of Mercury in Environmental Media and Human Exposure

PubMed Central

Kim, Moon-Kyung

2012-01-01

Mercury is emitted to the atmosphere from various natural and anthropogenic sources, and degrades with difficulty in the environment. Mercury exists as various species, mainly elemental (Hg0) and divalent (Hg2+) mercury depending on its oxidation states in air and water. Mercury emitted to the atmosphere can be deposited into aqueous environments by wet and dry depositions, and some can be re-emitted into the atmosphere. The deposited mercury species, mainly Hg2+, can react with various organic compounds in water and sediment by biotic reactions mediated by sulfur-reducing bacteria, and abiotic reactions mediated by sunlight photolysis, resulting in conversion into organic mercury such as methylmercury (MeHg). MeHg can be bioaccumulated through the food web in the ecosystem, finally exposing humans who consume fish. For a better understanding of how humans are exposed to mercury in the environment, this review paper summarizes the mechanisms of emission, fate and transport, speciation chemistry, bioaccumulation, levels of contamination in environmental media, and finally exposure assessment of humans. PMID:23230463

Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy.

PubMed

Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L

2014-08-30

The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Indirect effects of climate change on zinc cycling in sediments: The role of changing water levels.

PubMed

Nedrich, Sara M; Burton, G Allen

2017-09-01

Increased variability in lake and river water levels associated with changing climate could impact the fate and effects of metals in redox-sensitive sediments through the alteration of microbial communities and of acid-base and redox chemistry. The objective of the present study was to determine the influence of water level fluctuation on metal speciation in porewater and predict environmental risk to high-carbonate systems. Using experimental microcosms with sediments collected from 4 metal-contaminated coastal freshwater wetlands in Michigan, USA, we conducted water level fluctuation experiments. Porewater and sediment metals (Ca, Cu, Fe, Mg, Mn, Ni, Zn) and important metal binding phases (iron-oxide speciation, acid-volatile sulfide) were quantified. In a short-term drying (seiche) experiment, there were decreases in all porewater metals after inundation of saturated sediments. During a drought experiment, re-inundation of oxidized sediments increased porewater Cu, Zn, Mg, Ca for most sites. Porewater Zn increased after inundation to levels exceeding the US Environmental Protection Agency threshold for chronic toxicity. These data show that the dissolution of metal carbonates and metal sulfates contributes to metal release after re-flooding and indicate that we might expect increased ecological risk to organisms present in drought-sensitive regions where altered hydroperiods are likely to increase metal bioavailability. Environ Toxicol Chem 2017;36:2456-2464. © 2017 SETAC. © 2017 SETAC.

The Speciation of Silver Nanoparticles in Antimicrobial Fabric Before and After Exposure to a Hypochlorite/Detergent Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Impellitteri, Christopher A.; Tolaymat, Thabet M.; Scheckel, Kirk G.

2009-07-14

Because of their antibacterial properties, silver nanoparticles are often used in consumer products. To assess environmental and/or human health risks from these nanoparticles, there is a need to identify the chemical transformations that silver nanoparticles undergo in different environments. Thus an antimicrobial sock material containing Ag nanoparticles was examined by X-ray absorption spectroscopy to identify the speciation of Ag. The material was exposed to a hypochlorite/detergent solution and subjected to agitation. An elemental Ag nanopowder was also exposed to the hypochlorite/detergent solution or to a 1 mol L{sup -1} NaCl solution. Results showed that the sock material nanoparticles consisted ofmore » elemental Ag. After exposure to the hypochlorite/detergent solution, a significant portion (more than 50%) of the sock nanoparticles were converted, in situ, to AgCl. Results from exposures to elemental Ag nanopowder suggest that an oxidation step is necessary for the elemental Ag nanoparticles to transform into AgCl as there was no evidence of AgCl formation in the presence of chloride alone. As a result, if Ag ions leach from consumer products, any chloride present may quickly scavenge the ions. In addition, the efficacy of Ag, as an antimicrobial agent in fabrics, may be limited, or even negated, after washing in solutions containing oxidizers as AgCl is much less reactive than Ag ion.« less

Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

PubMed

Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; You, Shao-hong; Hu, Xi; Tan, Xiao-fei; Chen, An-wei; Guo, Fang-ying

2015-05-01

The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dissolved organic matter reduces CuO nanoparticle toxicity to duckweed in simulated natural systems.

PubMed

Rippner, Devin A; Green, Peter G; Young, Thomas M; Parikh, Sanjai J

2018-03-01

With increasing demand for recycled wastewater for irrigation purposes, there is a need to evaluate the potential for manufactured nanomaterials in waste water to impact crop production and agroecosystems. Copper oxide nanoparticles (CuO NPs) have previously been shown to negatively impact the growth of duckweed (Landoltia punctata) a model aquatic plant consumed by water fowl and widely found in agricultural runoff ditches in temperate climates. However, prior studies involving CuO NP toxicity to duckweed have focused on systems without the presence of dissolved organic matter (DOM). In the current study, duckweed growth inhibition was shown to be a function of aqueous Cu 2+ concentration. Growth inhibition was greatest from aqueous CuCl 2 and, for particles, increased with decreasing CuO particle size. The dissolution of CuO NPs in ½ Hoagland's solution was measured to increase with decreasing particle size and in the presence of Suwannee river humic and fulvic acids (HA; FA). However, the current results suggest that HA, and to a lesser extent, FA, decrease the toxicity of both CuO NPs and free ionized Cu to duckweed, likely by inhibiting Cu availability through Cu-DOM complex formation. Such results are consistent with changes to Cu speciation as predicted by speciation modeling software and suggest that DOM changes Cu speciation and therefore toxicity in natural systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Changes in iron, sulfur, and arsenic speciation associated with bacterial sulfate reduction in ferrihydrite-rich systems.

PubMed

Saalfield, Samantha L; Bostick, Benjamin C

2009-12-01

Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

Determination of the distribution and speciation of selenium in an argillaceous sample using chemical extractions and post-extractions analyses: application to the hydrogeological experimental site of Poitiers.

PubMed

Bassil, Joseph; Naveau, Aude; Bueno, Maïté; Di Tullo, Pamela; Grasset, Laurent; Kazpard, Véronique; Razack, Moumtaz

2016-05-01

To better understand selenium's dynamics in environmental systems, the present study aims to investigate selenium speciation and distribution in black argillaceous sediments, partially fulfilling karstic cavities into the Hydrogeological Experimental Site of Poitiers. These sediments are suspected to be responsible for selenium concentrations exceeding the European Framework Directive's drinking water limit value (10 μg L(-1)) in some specific wells. A combination of a sequential extractions scheme and single parallel extractions was thus applied on a representative argillaceous sample. Impacts of the extractions on mineral dissolution and organic matter mobilization were followed by quantifying major cations and total organic carbon (TOC) in the aqueous extracts. The nature of the released organic matter was characterized using thermochemolysis coupled with gas chromatography-mass spectrometry (GC-MS). About 10 % of selenium from the black argillaceous studied matrix could be defined as 'easily mobilizable' when the majority (around 70 %) revealed associated with the aliphatic and alkaline-soluble organic matter's fraction (about 20 %). In these fractions, selenium speciation was moreover dominated by oxidized species including a mixture of Se(VI) (20-30 %) and Se(IV) (70-80 %) in the 'easily mobilizable' fraction, while only Se(IV) was detected in alkaline-soluble organic matter fraction.

Automated Calibration of Atmospheric Oxidized Mercury Measurements.

PubMed

Lyman, Seth; Jones, Colleen; O'Neil, Trevor; Allen, Tanner; Miller, Matthieu; Gustin, Mae Sexauer; Pierce, Ashley M; Luke, Winston; Ren, Xinrong; Kelley, Paul

2016-12-06

The atmosphere is an important reservoir for mercury pollution, and understanding of oxidation processes is essential to elucidating the fate of atmospheric mercury. Several recent studies have shown that a low bias exists in a widely applied method for atmospheric oxidized mercury measurements. We developed an automated, permeation tube-based calibrator for elemental and oxidized mercury, and we integrated this calibrator with atmospheric mercury instrumentation (Tekran 2537/1130/1135 speciation systems) in Reno, Nevada and at Mauna Loa Observatory, Hawaii, U.S.A. While the calibrator has limitations, it was able to routinely inject stable amounts of HgCl 2 and HgBr 2 into atmospheric mercury measurement systems over periods of several months. In Reno, recovery of injected mercury compounds as gaseous oxidized mercury (as opposed to elemental mercury) decreased with increasing specific humidity, as has been shown in other studies, although this trend was not observed at Mauna Loa, likely due to differences in atmospheric chemistry at the two locations. Recovery of injected mercury compounds as oxidized mercury was greater in Mauna Loa than in Reno, and greater still for a cation-exchange membrane-based measurement system. These results show that routine calibration of atmospheric oxidized mercury measurements is both feasible and necessary.

AMS+ALS: Kinetic and Product Studies of the Heterogeneous Oxidation of Organic Aerosol at the Advanced Light Source

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Wilson, K. R.; Kessler, S. H.; Browne, E. C.; Nah, T.; Smith, J.; Worsnop, D. R.

2014-12-01

The atmospheric oxidation of condensed-phase organic species can have a major influence on the composition, properties, and impacts of organic aerosol (OA); however the rates and products of such "aging" reactions are poorly constrained. Here we describe a series of laboratory experiments aimed at better understanding one class of aging reactions, the heterogeneous oxidation of OA by gas-phase oxidants. Central to these experiments is the availability of vacuum ultraviolet (VUV) light at the Chemical Dynamics Beamline of the Advanced Light Source at LBNL, which enables the implementation of VUV photoionization aerosol mass spectrometry. This technique allows for the real-time, speciated measurement of OA composition, yielding molecular information that is highly complementary to ensemble data from electron-impact ionization. OA composition is measured with both ionization schemes as a function of oxidant exposure within a flow reactor, providing detailed information on the kinetics and products of heterogeneous oxidation over multiple generations of oxidation. Specific topics investigated include the branching between functionalization and fragmentation of OA components, the formation of secondary organic aerosol from photolytically-generated radical species, and the heterogeneous aging of soot-associated organic species.

Iron Speciation in Minerals and Melts at High Pressure: Implications for the Redox Evolution of the Early Mantle

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.; Miyajima, N.

2016-12-01

During the differentiation of the early Earth, the silicates of the mantle must have been in equilibrium with core-forming metal iron, as indicated by the depletion of siderophile elements from the mantle. Studies of ancient rocks suggest that by at least 3.9 Ga, the upper mantle was 4-5 log units more oxidized than metal saturation implies (Delano 2001). The process(es) by which the mantle was oxidized is unclear, but has implications for the timing of accretion, differentiation, and volatile delivery to the early Earth, as well as evolution of the early atmosphere. One plausible oxidation mechanism is suggested by the tendency of high-pressure silicate minerals to favor Fe3+ over Fe2+ in their structures, even at metal saturation. This preference in the lower mantle mineral bridgmanite has been proposed to drive the disproportionation reaction of FeO to form Fe­2O3 and iron metal (Frost and McCammon 2008). We have performed experiments at the Ru-RuO2 fO2 buffer which show that silicate melts may mirror this behavior and Fe3+ may be stabilized with pressure for a constant fO2; by 21 GPa, the previously observed trend of Fe3+ decreasing with pressure (O'Neill, 2006) reverses and ferric iron content had increased. If this is also the case at lower oxygen fugacities, FeO disproportionation may have occurred at the base of an early magma ocean, establishing a redox gradient similar to what is presumed for the mantle today. Here we report results of further multianvil and diamond anvil cell experiments exploring the plausibility of FeO disproportionation driving mantle oxidation. Experiments investigating Fe speciation in high pressure melts at variable fO2 will be discussed along with results of diamond anvil cell experiments investigating ferric iron content of lower mantle minerals at metal saturation.

Technical Evaluation of Biogeochemical Transformation of Iodine at 200-UP-1, Hanford, WA

NASA Astrophysics Data System (ADS)

Lee, M. H.; Cordova, E.; Brooks, S.; Moser, E.; Wells, J.; Lee, B.

2015-12-01

From the 1940s through the early 1990s, liquid wastes from materials used and produced at the Hanford Site were disposed to the ground through cribs, ditches, ponds, and trenches. Primary groundwater and vadose zone contaminants include carbon tetrachloride, uranium, nitrate, chromium, 129I, 99Tc, and tritium. Iodine-129 is of environmental concern due to its long half-life, mobility, and hazardous potential to humans through bioaccumulation, and is one of the primary risk drivers for the Hanford site. The 200 West area of the Hanford Site contains two separate plumes covering 1,500 acres where 129I concentrations are ~3.5 pCi/L in Hanford groundwater. Speciation analysis shows that iodate comprises 70.6% of the iodine present, and organo-iodide and iodide comprise 25.8% and 3.6% respectively. While hydraulic containment is the currently selected remedy for 129I in the groundwater, there is currently no remedy selected for controlling migration of 129I from the vadose zone to the groundwater. Research is currently underway to develop a site conceptual model for understanding the biogeochemical drivers for iodine speciation and determine the processes that drive the fate and transport of 129I through the vadose zone and into groundwater. These data will provide the information to decrease the uncertainty related to the inventory, distribution, and transport properties which will lead to appropriate treatment strategies for the 129I plume(s). Understanding the mechanisms and contributors to iodine speciation is important in order to develop bioremediation strategies for contaminated areas. The effect that microbial communities and humic acid have on iodine speciation and sorption was explored using Ringold sediment from the 200 West Area exposed to varying levels of 129I contamination in conjunction with varying growth media constituents. Several isolates obtained from these batch studies have been shown to reduce over 80% of iodate present in growth media when nitrate was present. No iodate reduction was observed in the absence of nitrate. Additionally, several isolates have been identified that can oxidize iodide. Currently, analytical techniques are underway to quantify the effect of microbial interaction on iodine speciation along with characterization of these diverse microbial isolates.

Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons.

PubMed

Isaacman, Gabriel; Chan, Arthur W H; Nah, Theodora; Worton, David R; Ruehl, Chris R; Wilson, Kevin R; Goldstein, Allen H

2012-10-02

Motor oil serves as a useful model system for atmospheric oxidation of hydrocarbon mixtures typical of anthropogenic atmospheric particulate matter, but its complexity often prevents comprehensive chemical speciation. In this work we fully characterize this formerly "unresolved complex mixture" at the molecular level using recently developed soft ionization gas chromatography techniques. Nucleated motor oil particles are oxidized in a flow tube reactor to investigate the relative reaction rates of observed hydrocarbon classes: alkanes, cycloalkanes, bicycloalkanes, tricycloalkanes, and steranes. Oxidation of hydrocarbons in a complex aerosol is found to be efficient, with approximately three-quarters (0.72 ± 0.06) of OH collisions yielding a reaction. Reaction rates of individual hydrocarbons are structurally dependent: compared to normal alkanes, reaction rates increased by 20-50% with branching, while rates decreased ∼20% per nonaromatic ring present. These differences in rates are expected to alter particle composition as a function of oxidation, with depletion of branched and enrichment of cyclic hydrocarbons. Due to this expected shift toward ring-opening reactions heterogeneous oxidation of the unreacted hydrocarbon mixture is less likely to proceed through fragmentation pathways in more oxidized particles. Based on the observed oxidation-induced changes in composition, isomer-resolved analysis has potential utility for determining the photochemical age of atmospheric particulate matter with respect to heterogeneous oxidation.

Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

PubMed

Clark, Christopher H; Kacarab, Mary; Nakao, Shunsuke; Asa-Awuku, Akua; Sato, Kei; Cocker, David R

2016-06-07

Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided.

Reversed Phase Column HPLC-ICP-MS Conditions for Arsenic Speciation Analysis of Rice Flour.

PubMed

Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

2015-01-01

New measurement conditions for arsenic speciation analysis of rice flour were developed using HPLC-ICP-MS equipped with a reversed phase ODS column. Eight arsenic species, namely, arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA), arsenobetaine (AsB) and arsenocholine (AsC), were separated and determined under the proposed conditions. In particular, As(III) and MMAA and DMAA and AsB were completely separated using a newly proposed eluent containing ammonium dihydrogen phosphate. Importantly, the sensitivity changes, in particular those of As(V) and As(III) caused by coexisting elements and by complex matrix composition, which had been problematical in previously reported methods, were eliminated. The new eluent can be applied to C8, C18 and C30 ODS columns with the same effectiveness and with excellent repeatability. The proposed analytical method was successfully applied to extracts of rice flour certified reference materials.

Ce, Ti modified MCM-48 mesoporous photocatalysts: Effect of the synthesis route on support and metal ion properties

NASA Astrophysics Data System (ADS)

Mureseanu, Mihaela; Filip, Mihaela; Somacescu, Simona; Baran, Adriana; Carja, Gabriela; Parvulescu, Viorica

2018-06-01

New Ti-MCM-48 and CeTi-MCM-48 photocatalysts were obtained by impregnation of the MCM-48 silica support synthesized by a hydrothermal process with aqueous solution of Ti and Ce precursors. The immobilization of metal cations presented a low effect on the porosity, morphology and structure of MCM-48 mesoporous silica support as was evidenced by N2 adsorption-desorption, X-ray diffraction, SEM and TEM electron microscopy. EDAX analysis and X-ray photoelectron microscopy (XPS) indicated that titanium cations were present on the mesoporous silica surface only as Ti4+ species and the effect of ceria on titanium speciation was different, compared to the CeTi-MCM-48 sample, previously obtained by direct synthesis. The photocatalytic properties of mono- and bimetallic catalysts were evaluated in degradation of phenol from water and correlated with the active metallic species concentration, distribution, speciation and their interaction with the support or each other. An advanced oxidation mechanism for phenol degradation by radical species was proposed.

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

NASA Astrophysics Data System (ADS)

Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

2003-04-01

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

Concentrations and speciation of arsenic along a groundwater flow-path in the Upper Floridan aquifer, Florida, USA

NASA Astrophysics Data System (ADS)

Haque, S. E.; Johannesson, K. H.

2006-05-01

Arsenic (As) concentrations and speciation were determined in groundwaters along a flow-path in the Upper Floridan aquifer (UFA) to investigate the biogeochemical “evolution“ of As in this relatively pristine aquifer. Dissolved inorganic As species were separated in the field using anion-exchange chromatography and subsequently analyzed by inductively coupled plasma mass spectrometry. Total As concentrations are higher in the recharge area groundwaters compared to down-gradient portions of UFA. Redox conditions vary from relatively oxic to anoxic along the flow-path. Mobilization of As species in UFA groundwaters is influenced by ferric iron reduction and subsequent dissolution, sulfate reduction, and probable pyrite precipitation that are inferred from the data to occur along distinct regions of the flow-path. In general, the distribution of As species are consistent with equilibrium thermodynamics, such that arsenate dominates in more oxidizing waters near the recharge area, and arsenite predominates in the progressively reducing groundwaters beyond the recharge area.

Bioaccumulation and biotransformation of arsenic compounds in Hediste diversicolor (Muller 1776) after exposure to spiked sediments.

PubMed

Gaion, Andrea; Sartori, Davide; Scuderi, Alice; Fattorini, Daniele

2014-05-01

This study focused on the exposure of the common ragworm Hediste diversicolor (Müller 1776) to sediments enriched with different arsenic compounds, namely arsenate, dimethyl-arsinate, and arsenobetaine. Speciation analysis was carried out on both the spiked sediments and the exposed polychaetes in order to investigate H. diversicolor capability of arsenic bioaccumulation and biotransformation. Two levels of contamination (acute and moderate dose) were chosen for enriched sediments to investigate possible differences in the arsenic bioaccumulation patterns. The highest value of arsenic in tissues was reached after 15 days of exposure to dimethyl-arsinate (acute dose) spiked sediment (1,172 ± 176 μg/g). A significant increase was also obtained in worms exposed both to arsenate and arsenobetaine. Speciation analysis showed that trimethyl-arsine oxide was the predominant chemical form in tissues of H. diversicolor exposed to all the spiked sediments, confirming the importance of this intermediate in biological transformation of arsenic.

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

DOE PAGES

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; ...

2017-05-19

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less

High-time resolved measurements of biogenic and anthropogenic secondary organic aerosol precursors and products in urban air

NASA Astrophysics Data System (ADS)

Flores, Rosa M.; Doskey, Paul V.

2016-04-01

Volatile organic compounds (VOCs), which are present in the atmosphere entirely in the gas phase are directly emitted by biogenic (~1089 Tg yr-1) and anthropogenic sources (~185 Tg yr-1). However, the sources and molecular speciation of intermediate VOCs (IVOCs), which are for the most part also present almost entirely in the gas phase, are not well characterized. The VOCs and IVOCs participate in reactions that form ozone and semivolatile OC (SVOC) that partition into the aerosol phase. Formation and evolution of secondary organic aerosol (SOA) are part of a complex dynamic process that depends on the molecular speciation and concentration of VOCs, IVOCs, primary organic aerosol (POA), and the level of oxidants (NO3, OH, O3). The current lack of understanding of OA properties and their impact on radiative forcing, ecosystems, and human health is partly due to limitations of models to predict SOA production on local, regional, and global scales. More accurate forecasting of SOA production requires high-temporal resolution measurement and molecular characterization of SOA precursors and products. For the subject study, the IVOCs and aerosol-phase organic matter were collected using the high-volume sampling technique and were analyzed by multidimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToFMS). The IVOCs included terpenes, terpenoids, n-alkanes, branched alkanes, isoprenoids, alkylbenzenes, cycloalkylbenzenes, PAH, alkyl PAH, and an unresolved complex mixture (UCM). Diurnal variations of OA species containing multiple oxygenated functionalities and selected SOA tracers of isorprene, α-pinene, toluene, cyclohexene, and n-dodecane oxidation were also quantified. The data for SOA precursor and oxidation products presented here will be useful for evaluating the ability of molecular-specific SOA models to forecast SOA production in and downwind of urban areas.

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

NASA Astrophysics Data System (ADS)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

2017-08-01

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

40 CFR 58.10 - Annual monitoring network plan and periodic network assessment.

Code of Federal Regulations, 2012 CFR

2012-07-01

... part of SLAMS, NCore stations, STN stations, State speciation stations, SPM stations, and/or, in... analysis method(s) for each measured parameter. (4) The operating schedules for each monitor. (5) Any...

40 CFR 58.10 - Annual monitoring network plan and periodic network assessment.

Code of Federal Regulations, 2013 CFR

2013-07-01

... part of SLAMS, NCore stations, STN stations, State speciation stations, SPM stations, and/or, in... and analysis method(s) for each measured parameter. (4) The operating schedules for each monitor. (5...

40 CFR 58.10 - Annual monitoring network plan and periodic network assessment.

Code of Federal Regulations, 2014 CFR

2014-07-01

... part of SLAMS, NCore stations, STN stations, State speciation stations, SPM stations, and/or, in... and analysis method(s) for each measured parameter. (4) The operating schedules for each monitor. (5...

Volatile and semivolatile organic compounds in laboratory ...

EPA Pesticide Factsheets

Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particulate organics were quantified by gas chromatography/mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (~60 %) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. Speciated organic PM2.5 mass was dominated by the following compound classes: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for PM2.5 organic acids including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12 %) of all speciated compound classes measured in this work. Levoglucosan contributed 2-3 % of the OC mass, while methoxyphenols represented 0.2-0.3 % of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon. Total HAP VOC and particulate polycyclic aromatic hydrocarbon emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions. This p

The flotation tailings of the former Pb-Zn mine of Touiref (NW Tunisia): mineralogy, mine drainage prediction, base-metal speciation assessment and geochemical modeling.

PubMed

Othmani, Mohamed Ali; Souissi, Fouad; Bouzahzah, Hassan; Bussière, Bruno; da Silva, Eduardo Ferreira; Benzaazoua, Mostafa

2015-02-01

The underground extraction of Pb-Zn mineralization in the Touiref area stopped in 1958. A large volume of flotation tailings (more than 500 Mt) containing sulfides were deposited in a tailings impoundment. The goals of this study are to evaluate the neutralization capacity of the unoxidized and oxidized tailings, to assess the speciation of metals between the different components of the tailings material, and to assess the mobility of metals and the secondary minerals' precipitation in pore waters using geochemical modeling. To accomplish these objectives, representative samples from both fresh and oxidized zones were collected along a vertical profile through the tailings pile. Physical, chemical (ICP-MS), and mineralogical characterization (X-ray diffraction (XRD), reflected light microscopy, scanning electron microscope (SEM)) of these samples was performed. Grain size analysis shows that the tailings are dominated by silt- to sand-sized fractions. The microscopic observation highlights the presence of pyrite, marcasite, galena, and sphalerite as primary minerals in a carbonated matrix. The study reveals also the presence of secondary minerals represented by cerussite, smithsonite, anglesite, and Fe oxi-hydroxides as important scavengers for trace elements. The static tests show that the presence of calcite in the tailing samples ensures acid-neutralizing capacity (ANC), which is significantly greater than the acidity potential (PA). The geochemical characterization of the unoxidized samples shows higher Cd, Pb, and Zn concentrations than the oxidized samples containing the highest values for Fe and SO4. Sequential extraction tests show that significant percentages of metals are distributed between the acid-soluble fractions (Cd, Pb, and Zn) and the reducible one (Zn). Pore water analysis indicates that Ca is the dominant cation (8,170 and 6,200 mg L(-1), respectively), whereas sulfate is the principal anion (6,900 and 5,100 mg L(-1), respectively). Saturation index (SI) calculations of minerals in pore water extracted from both the oxidized and unoxidized samples are indicative of gypsum (SI >0) and Fe(III) oxides (SI ≫0) precipitation. The latter controls the Fe concentration in solution.

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones.

PubMed

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-12-16

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ 66 Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ 66 Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO 4 2- complexes preferentially incorporate heavy δ 66 Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge.

Copper speciation in variably toxic sediments at the Ely Copper Mine, Vermont, United States

USGS Publications Warehouse

Kimball, Bryn E.; Foster, Andrea L.; Seal, Robert R.; Piatak, Nadine M.; Webb, Samuel M.; Hammarstrom, Jane M.

2016-01-01

At the Ely Copper Mine Superfund site, Cu concentrations exceed background values in both streamwater (160–1200 times) and sediments (15–79 times). Previously, these sediment samples were incubated with laboratory test organisms, and they exhibited variable toxicity for different stream sites. In this study we combined bulk- and microscale techniques to determine Cu speciation and distribution in these contaminated sediments on the basis of evidence from previous work that Cu was the most important stressor in this environment and that variable observed toxicity could have resulted from differences in Cu speciation. Copper speciation results were similar at microscopic and bulk scales. The major Cu species in the more toxic samples were sorbed or coprecipitated with secondary Mn (birnessite) and Fe minerals (jarosite and goethite), which together accounted for nearly 80% of the total Cu. The major Cu species in the less toxic samples were Cu sulfides (chalcopyrite and a covellite-like phase), making up about 80–95% of the total Cu, with minor amounts of Cu associated with jarosite or goethite. These Cu speciation results are consistent with the toxicity results, considering that Cu sorbed or coprecipitated with secondary phases at near-neutral pH is relatively less stable than Cu bound to sulfide at lower pH. The more toxic stream sediment sites were those that contained fewer detrital sulfides and were upstream of the major mine waste pile, suggesting that removal and consolidation of sulfide-bearing waste piles on site may not eliminate all sources of bioaccessible Cu.

Enrichment mechanisms of tellurium in ferromanganese crusts

NASA Astrophysics Data System (ADS)

Sakaguchi, A.; Sugiyama, T.; Usui, A.; Takahashi, Y.

2012-04-01

Marine ferromanganese crusts (FMCs) consist of iron (Fe) hydroxides and manganese (Mn) oxides with various minor and trace elements. Especially for tellurium (Te), which is recognized as one of the rare metals, it has been reported that this element is concentrated about 105 times in FMCs compared with earth's crust, and the host phase might be Fe (oxy)hydroxide (Hein et al., 2003). Actually, in our previous study, the high concentration of Te in very surface layers of FMCs was found from the top to halfway down of a seamount in the Pacific Ocean. However, the concentration of Te in surface layers through the seamount showed good correlation with that of Mn instead of Fe. In this study, we attempted to clarify the enrichment mechanism of Te in FMCs with some methods including X-ray absorption fine structure (XAFS) technique for synthesised /natural samples. Seventeen FMC samples were collected from the Takuyo-Daigo seamount, from 950 m (summit) to 3000 m in water depth, with hyper-dolphin (remotely operated vehicle) equipped with live video camera and manipulators. The growth rates of all FMC samples were estimated to be about 3 mm/Ma. Very surface layer (less than 1 mm) of all FMC was analyzed with XRD and XAFS to confirm the mineral composition and speciation of Te. Furthermore, to serve as an aid to clarify the adsorption mechanism of Te on FMCs, distribution coefficients (Kd) and oxidation states were determined through the adsorption experiments of Te(IV) and Te(VI) on ferrihydrite and δ-MnO2. In all the experiments, pH and ionic strength were adjusted to pH 7.5 and 0.7 M, respectively. The oxidation state of Te in water phase was determined with HPLC-ICP-MS. As for the analysis of oxidation and adsorption states on the solid phase, XAFS was employed. The major mineral composition of Fe and Mn had no significant variation through the water depth of Takuyo-Daigo seamount. The oxidation state of Te in all samples showed hexavalent, and there was no significant difference of adsorption state independent of the DO, salinity and temperature in water. It has been reported that Te exists as tetravalent and hexavalent in sea water of the Pacific Ocean (Nozaki, 1996). Thus, it can be said that the Te in sea water is oxidised and incorporated into FMCs. As a result of the adsorption experiments in laboratory, the Kd of Te on ferrihydrite was larger than that of δ-MnO2, and Te(IV) was adsorbed to a larger degree than Te(VI) on both minerals. The adsorption experiments of Te(IV) on δ-MnO2 showed that the solid phase has only hexavalent Te, although the water phase has both tetra and hexavalent species of Te. Te(IV) on ferrihydrite was not oxidized to Te(VI). From these results, it can be suggested that Te(IV) was oxidized by δ-MnO2 and would be adsorbed onto ferrihydrite. Actually, the results of double-cell adsorption experiments support this hypothesis. The detail of our results and discussion will be given in the presentation.

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

Method for removal and stabilization of mercury in mercury-containing gas streams

DOEpatents

Broderick, Thomas E.

2005-09-13

The present invention is directed to a process and apparatus for removing and stabilizing mercury from mercury-containing gas streams. A gas stream containing vapor phase elemental and/or speciated mercury is contacted with reagent, such as an oxygen-containing oxidant, in a liquid environment to form a mercury-containing precipitate. The mercury-containing precipitate is kept or placed in solution and reacts with one or more additional reagents to form a solid, stable mercury-containing compound.

COMPARISON OF DATA FROM THE STN AND IMPROVE NETWORKS

EPA Science Inventory

Two national chemical speciation-monitoring networks operate currently within the United States. The Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network operates primarily in rural areas collecting aerosol and optical data to better understand th...

Driving south: a multi-gene phylogeny of the brown algal family Fucaceae reveals relationships and recent drivers of a marine radiation.

PubMed

Cánovas, Fernando G; Mota, Catarina F; Serrão, Ester A; Pearson, Gareth A

2011-12-21

Understanding the processes driving speciation in marine ecosystems remained a challenge until recently, due to the unclear nature of dispersal boundaries. However, recent evidence for marine adaptive radiations and ecological speciation, as well as previously undetected patterns of cryptic speciation is overturning this view. Here, we use multi-gene phylogenetics to infer the family-level evolutionary history of Fucaceae (intertidal brown algae of the northern Pacific and Atlantic) in order to investigate recent and unique patterns of radiative speciation in the genus Fucus in the Atlantic, in contrast with the mainly monospecific extant genera. We developed a set of markers from 13 protein coding genes based on polymorphic cDNA from EST libraries, which provided novel resolution allowing estimation of ancestral character states and a detailed reconstruction of the recent radiative history. Phylogenetic reconstructions yielded similar topologies and revealed four independent trans-Arctic colonization events by Fucaceae lineages, two of which also involved transitions from hermaphroditism to dioecy associated with Atlantic invasions. More recently, reversion of dioecious ancestral lineages towards hermaphroditism has occurred in the genus Fucus, particularly coinciding with colonization of more extreme habitats. Novel lineages in the genus Fucus were also revealed in association with southern habitats. These most recent speciation events occurred during the Pleistocene glaciations and coincided with a shift towards selfing mating systems, generally southward shifts in distribution, and invasion of novel habitats. Diversification of the family occurred in the Late-Mid Miocene, with at least four independent trans-Artic lineage crossings coincident with two reproductive mode transitions. The genus Fucus arose in the Pliocene but radiated within a relatively short time frame about 2.5 million years ago. Current species distributions of Fucus suggest that climatic factors promoted differentiation between the two major clades, while the recent and rapid species radiation in the temperate clade during Pleistocene glacial cycles coincided with several potential speciation drivers.

Hydrogen ion speciation in the acid precipitation of the northeastern United States

Treesearch

James N. Galloway; Gene E. Likens; Eric S. Edgerton

1976-01-01

The acidity of precipitation in rural, forested areas of the northeastern United States is dominated by the strong mineral acids, sulfuric and nitric. Weak acids have a negligible effect on the measured acidity (pH) of precipitation. These conclusions are based on total acidity titrations and detailed analysis of organic and inorganic components in precipitation.

Visualizing speciation in artificial cichlid fish.

PubMed

Clement, Ross

2006-01-01

The Cichlid Speciation Project (CSP) is an ALife simulation system for investigating open problems in the speciation of African cichlid fish. The CSP can be used to perform a wide range of experiments that show that speciation is a natural consequence of certain biological systems. A visualization system capable of extracting the history of speciation from low-level trace data and creating a phylogenetic tree has been implemented. Unlike previous approaches, this visualization system presents a concrete trace of speciation, rather than a summary of low-level information from which the viewer can make subjective decisions on how speciation progressed. The phylogenetic trees are a more objective visualization of speciation, and enable automated collection and summarization of the results of experiments. The visualization system is used to create a phylogenetic tree from an experiment that models sympatric speciation.

Particulate matter speciation profiles for light-duty gasoline vehicles in the United States.

PubMed

Sonntag, Darrell B; Baldauf, Richard W; Yanca, Catherine A; Fulper, Carl R

2014-05-01

Representative profiles for particulate matter particles less than or equal to 2.5 microm (PM2.5) are developed from the Kansas City Light-Duty Vehicle Emissions Study for use in the US. Environmental Protection Agency (EPA) vehicle emission model, the Motor Vehicle Emission Simulator (MOVES), and for inclusion in the EPA SPECIATE database for speciation profiles. The profiles are compatible with the inputs of current photochemical air quality models, including the Community Multiscale Air Quality Aerosol Module Version 6 (AE6). The composition of light-duty gasoline PM2.5 emissions differs significantly between cold start and hot stabilized running emissions, and between older and newer vehicles, reflecting both impacts of aging/deterioration and changes in vehicle technology. Fleet-average PM2.5 profiles are estimated for cold start and hot stabilized running emission processes. Fleet-average profiles are calculated to include emissions from deteriorated high-emitting vehicles that are expected to continue to contribute disproportionately to the fleet-wide PM2.5 emissions into the future. The profiles are calculated using a weighted average of the PM2.5 composition according to the contribution of PM2.5 emissions from each class of vehicles in the on-road gasoline fleet in the Kansas City Metropolitan Statistical Area. The paper introduces methods to exclude insignificant measurements, correct for organic carbon positive artifact, and control for contamination from the testing infrastructure in developing speciation profiles. The uncertainty of the PM2.5 species fraction in each profile is quantified using sampling survey analysis methods. The primary use of the profiles is to develop PM2.5 emissions inventories for the United States, but the profiles may also be used in source apportionment, atmospheric modeling, and exposure assessment, and as a basis for light-duty gasoline emission profiles for countries with limited data. PM2.5 speciation profiles were developed from a large sample of light-duty gasoline vehicles tested in the Kansas City area. Separate PM2.5 profiles represent cold start and hot stabilized running emission processes to distinguish important differences in chemical composition. Statistical analysis was used to construct profiles that represent PM2.5 emissions from the U.S. vehicle fleet based on vehicles tested from the 2005 calendar year Kansas City metropolitan area. The profiles have been incorporated into the EPA MOVES emissions model, as well as the EPA SPECIATE database, to improve emission inventories and provide the PM2.5 chemical characterization needed by CMAQv5.0 for atmospheric chemistry modeling.

Transcriptomic Responses During Early Development Following Arsenic Exposure in Western Clawed Frogs, Silurana tropicalis.

PubMed

Zhang, Jing; Koch, Iris; Gibson, Laura A; Loughery, Jennifer R; Martyniuk, Christopher J; Button, Mark; Caumette, Guilhem; Reimer, Kenneth J; Cullen, William R; Langlois, Valerie S

2015-12-01

Arsenic compounds are widespread environmental contaminants and exposure elicits serious health issues, including early developmental anomalies. Depending on the oxidation state, the intermediates of arsenic metabolism interfere with a range of subcellular events, but the fundamental molecular events that lead to speciation-dependent arsenic toxicity are not fully elucidated. This study therefore assesses the impact of arsenic exposure on early development by measuring speciation and gene expression profiles in the developing Western clawed frog (Silurana tropicalis) larvae following the environmental relevant 0.5 and 1 ppm arsenate exposure. Using HPLC-ICP-MS, arsenate, dimethylarsenic acid, arsenobetaine, arsenocholine, and tetramethylarsonium ion were detected. Microarray and pathway analyses were utilized to characterize the comprehensive transcriptomic responses to arsenic exposure. Clustering analysis of expression data showed distinct gene expression patterns in arsenate treated groups when compared with the control. Pathway enrichment revealed common biological themes enriched in both treatments, including cell signal transduction, cell survival, and developmental pathways. Moreover, the 0.5 ppm exposure led to the enrichment of pathways and biological processes involved in arsenic intake or efflux, as well as histone remodeling. These compensatory responses are hypothesized to be responsible for maintaining an in-body arsenic level comparable to control animals. With no appreciable changes observed in malformation and mortality between control and exposed larvae, this is the first study to suggest that the underlying transcriptomic regulations related to signal transduction, cell survival, developmental pathways, and histone remodeling may contribute to maintaining ongoing development while coping with the potential arsenic toxicity in S. tropicalis during early development. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Metallomics for drug development: a further insight into intracellular activation chemistry of a ruthenium(III)-based anticancer drug gained using a multidimensional analytical approach.

PubMed

Matczuk, Magdalena; Prządka, Monika; Aleksenko, Svetlana S; Czarnocki, Zbigniew; Pawlak, Katarzyna; Timerbaev, Andrei R; Jarosz, Maciej

2014-01-01

The mechanism by which the most relevant ruthenium anticancer drugs are activated in tumors to commence their tumor-inhibiting action remains one of the challenging research tasks of present-day metallomics. This contribution aims to capture and identify eventually more reactive species of one of two bis-indazole tetrachloridoruthenate(III) compounds that are progressing in clinical trials. In view of the fact that the transport of ruthenium into cancer cells is governed by transferrin receptors, the susceptibility of the Ru drug adduct with holo-transferrin to exposure by glutathione and ascorbic acid (at their cancer cytosol concentrations) was studied by inductively coupled plasma mass spectrometry (ICP-MS), following isolation of the reaction products by ultrafiltration. Next, capillary electrophoresis coupled to ICP-MS was applied to monitor changes in the Ru speciation both under simulated cancer cytosol conditions and in real cytosol and to assign the charge state of novel metal species. The latter were identified by using tandem electrospray ionization MS in the respective ion mode. The formation of ruthenium(II) species was for the first time revealed, in which the central metal is coordinated by the reduced (GSH) or the oxidized (GSSG) form of glutathione, i.e. [Ru(II)HindCl4(GSH)](2-) and [Ru(II)HindCl4(GSSG)](2-), respectively (Hind = indazole). Ascorbic acid released the ruthenium functionality from the protein-bound form in a different way, the products of adduct cleavage containing aqua ligands. Distribution of low-molecular mass species of Ru in human cytosol was found to have very much in common with the ruthenium speciation assayed under simulated cytosol conditions.

Assessment of primary and secondary ambient particle trends using satellite aerosol optical depth and ground speciation data in the New England region, United States

PubMed Central

Lee, Hyung Joo; Kang, Choong-Min; Coull, Brent A.; Bell, Michelle L.; Koutrakis, Petros

2014-01-01

The effectiveness of air pollution emission control policies can be evaluated by examining ambient pollutant concentration trends that are observed at a large number of ground monitoring sites over time. In this paper, we used ground monitoring measurements in conjunction with satellite aerosol optical depth (AOD) data to investigate fine particulate matter (PM2.5; particulate matter with aerodynamic diameter ≤2.5 μm) trends and their spatial patterns over a large U.S. region, New England, during 2000–2008. We examined the trends in rural and urban areas to get a better insight about the trends of regional and local source emissions. Decreases in PM2.5 concentrations (μg/m3) were more pronounced in urban areas than in rural ones. In addition, the highest and lowest PM2.5 decreases (μg/m3) were observed for winter and summer, respectively. Together, these findings suggest that primary particle concentrations decreased more relative to secondary ones. This is also supported by the analysis of the speciation data which showed that downward trends of primary pollutants including black carbon were stronger than those of secondary pollutants including sulfate. Furthermore, this study found that ambient primary pollutants decreased at the same rate as their respective source emissions. This was not the case for secondary pollutants which decreased at a slower rate than that of their precursor emissions. This indicates that concentrations of secondary pollutants depend not only on the primary emissions but also on the availability of atmospheric oxidants which might not change during the study period. This novel approach of investigating spatially varying concentration trends, in combination with ground PM2.5 species trends, can be of substantial regulatory importance. PMID:24906074

Atmospheric mercury and fine particulate matter in coastal New England: implications for mercury and trace element sources in the northeastern United States

USGS Publications Warehouse

Kolker, Allan; Engle, Mark A.; Peucker-Ehrenbrink, Bernhard; Geboy, Nicholas J.; Krabbenhotft, David P.; Bothner, Michael H.; Tate, Michael T.

2013-01-01

Intensive sampling of ambient atmospheric fine particulate matter was conducted at Woods Hole, Massachusetts over a four-month period from 3 April to 29 July, 2008, in conjunction with year-long deployment of the USGS Mobile Mercury Lab. Results were obtained for trace elements in fine particulate matter concurrently with determination of ambient atmospheric mercury speciation and concentrations of ancillary gasses (SO2, NOx, and O3). For particulate matter, trace element enrichment factors greater than 10 relative to crustal background values were found for As, Bi, Cd, Cu, Hg, Pb, Sb, V, and Zn, indicating contribution of these elements by anthropogenic sources. For other elements, enrichments are consistent with natural marine (Na, Ca, Mg, Sr) or crustal (Ba, Ce, Co, Cs, Fe, Ga, La, Rb, Sc, Th, Ti, U, Y) sources, respectively. Positive matrix factorization was used together with concentration weighted air-mass back trajectories to better define element sources and their locations. Our analysis, based on events exhibiting the 10% highest PM2.5 contributions for each source category, identifies coal-fired power stations concentrated in the U.S. Ohio Valley, metal smelting in eastern Canada, and marine and crustal sources showing surprisingly similar back trajectories, at times each sampling Atlantic coastal airsheds. This pattern is consistent with contribution of Saharan dust by a summer maximum at the latitude of Florida and northward transport up the Atlantic Coast by clockwise circulation of the summer Bermuda High. Results for mercury speciation show diurnal production of RGM by photochemical oxidation of Hg° in a marine environment, and periodic traverse of the study area by correlated RGM-SO2(NOx) plumes, indicative of coal combustion sources.

Speciation and Elemental Mapping of Metal Containing Aerosols

NASA Astrophysics Data System (ADS)

Fraund, M. W.; Moffet, R.; Harder, T.; Williams, G.; Chen-Wiegart, Y. C. K.; Laskin, A.; Gilles, M. K.; Schoonen, M. A.; Thieme, J.

2017-12-01

Transition metals play a key roles in biogeochemical processes and health effects of aerosols. The Submicron Resolution X-ray (SRX) beamline at the second National Synchrotron Light Source (NSLS-II) can be used to obtain spatially resolved elemental composition using X-ray fluorescence (XRF) as well as element specific molecular information through X-ray absorption near edge structure (XANES) spectroscopy. Here, XANES spectroscopy was used to identify the oxidation state of iron-rich particles collected from the Cape Hedo Observatory on the island of Okinawa, Japan which is subject to aerosols from both biogenic (Gobi desert) and anthropogenic sources (e.g. Beijing and Shanghai). This data was compared with standards to help classify the minerology and source of these aerosol particles with regards to their potential solubility and bioavailability. In another application of the XRF/XANES measurements from NSLS-II, Pb rich particles from Mexico City were probed for distribution and speciation of Pb. Prior study has indicated that elevated concentrations of Pb occur in an industrialized section of northern Mexico City. It has been established that Pb and Zn are internally mixed in atmospheric aerosol and that Zn primarily exists as ZnCl2 and Zn(NO3)2. Based on these observations, it is hypothesized that Pb also exists as PbCl2 and Pb(NO3)­2. In this study it is shown that X-ray absorption near edge structure (XANES) spectroscopy at the Pb L-edge supports Pb being present as PbCl2 and Pb(NO3)2. Submicron resolution X-ray fluorescence mapping is also used to provide complimentary information on the collocation of other high-Z elements.

Comparative tests of the role of dewlap size in Anolis lizard speciation

PubMed Central

Harrison, Alexis; Mahler, D. Luke; Castañeda, María del Rosario; Glor, Richard E.; Herrel, Anthony; Stuart, Yoel E.; Losos, Jonathan B.

2016-01-01

Phenotypic traits may be linked to speciation in two distinct ways: character values may influence the rate of speciation or diversification in the trait may be associated with speciation events. Traits involved in signal transmission, such as the dewlap of Anolis lizards, are often involved in the speciation process. The dewlap is an important visual signal with roles in species recognition and sexual selection, and dewlaps vary among species in relative size as well as colour and pattern. We compile a dataset of relative dewlap size digitized from photographs of 184 anole species from across the genus' geographical range. We use phylogenetic comparative methods to test two hypotheses: that larger dewlaps are associated with higher speciation rates, and that relative dewlap area diversifies according to a speciational model of evolution. We find no evidence of trait-dependent speciation, indicating that larger signals do not enhance any role the dewlap has in promoting speciation. Instead, we find a signal of mixed speciational and gradual trait evolution, with a particularly strong signal of speciational change in the dewlaps of mainland lineages. This indicates that dewlap size diversifies in association with the speciation process, suggesting that divergent selection may play a role in the macroevolution of this signalling trait. PMID:28003450

Arsenic release and speciation during the oxidative dissolution of arsenopyrite by O2 in the absence and presence of EDTA.

PubMed

Wang, Shaofeng; Jiao, BeiBei; Zhang, Mingmei; Zhang, Guoqing; Wang, Xin; Jia, Yongfeng

2018-03-15

The oxidative decomposition of arsenopyrite is an important source of As in surface environment. This study investigated the oxidative dissolution of arsenopyrite by O 2 and aqueous arsenic transformation at different pHs, dissolved oxygen (DO) contents, and temperatures in the absence and presence of EDTA. The oxidative dissolution was greatly inhibited at neutral and alkaline pH in the absence of EDTA. However, in the presence of EDTA, the oxidative dissolution rate increased linearly from pH 4 to 7. The highest dissolution rate was 3-4 times higher than that at pH 4 and 1-2 orders of magnitude higher than that at pH 7 in the absence of EDTA. This is possibly due to the lack of Fe oxyhydroxides on the surface of arsenopyrite. In the pH range of 7-10, the oxidative dissolution rate decreased linearly, possibly due to the formation of goethite and/or hematite coating. The oxidation of released arsenite (As III ) to arsenate (As V ) took place simultaneously during the oxidative dissolution of arsenopyrite in the presence of dissolved Fe without EDTA, while no obvious aqueous As III oxidation was observed in the presence of EDTA, indicating that aqueous Fe species play an important role in As III oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

Geomicrobiological cycling of antimony

NASA Astrophysics Data System (ADS)

Kulp, T. R.; Terry, L.; Dovick, M. A.; Braiotta, F.

2013-12-01

Microbiologically catalyzed oxidation and reduction of toxic metalloids (e.g., As, Se, and Te) generally proceeds much faster than corresponding abiotic reactions. These microbial transformations constitute biogeochemical cycles that control chemical speciation and environmental behavior of metalloids in aqueous environments. Particular progress has been made over the past two decades in documenting microbiological biotransformations of As, which include anaerobic respiratory reduction of As(V) to As(III), oxidation of As(III) to As(V) linked to chemoautotrophy or photoautotrophy, and cellular detoxification pathways. By contrast, microbial interactions with Sb, As's group 15 neighbor and a toxic element of emerging global concern, are poorly understood. Our work with sediment microcosms, enrichment cultures, and bacterial isolates suggests that prokaryotic metabolisms may be similarly important to environmental Sb cycling. Enrichment cultures and isolates from a Sb-contaminated mine site in Idaho exhibited Sb(V)-dependent heterotrophic respiration under anaerobic conditions and Sb(III)-dependent autotrophic growth in the presence of air. Live, anoxic cultures reduced 2 mM Sb(V) to Sb(III) within 5 d, while no activity occurred in killed controls. Sb(V) reduction was stimulated by lactate or acetate and was quantitatively coupled to the oxidation of lactate. The oxidation of radiolabeled 14C-acetate (monitored by GC-GPC) demonstrated Sb(V)-dependent oxidation to 14CO2, suggesting a dissimilatory process. Sb(V) dependent growth in cultures was demonstrated by direct counting. Microbiological reduction of Sb(V) also occurred in anerobic sediment microcosms from an uncontaminated suburban lake, but did not appear to be linked to growth and is interpreted as a mechanism of biological detoxification. Aerobic microcosms and cultures from the Idaho mine oxidized 2 mM Sb(III) to Sb(V) within 7 d and coupled this reaction to cell growth quantified by direct counting. An anoxygenic photosynthetic community of purple sulfur bacteria from Pyramid Lake, NV, however, that was capable of growth via anoxygenic photosynthesis using As(III) as an electron donor was not capable of similar growth using Sb(III). These results suggest that geomicrobiological Sb cycling is an important influence on the environmental speciation and behavior of Sb, and portend the presence of a global biogeochemical Sb cycle that is analogous to but distinct from that for As.

EPA’s SPECIATE 4.4 Database:Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

EPA’s SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

Determination of chemical speciations of cerium in nuclear waste glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Meiling; Li, Hong

1996-12-31

Cerium oxides have been widely used as a surrogate for plutonium in the investigation of the melt and durability behavior of simulated nuclear waste glasses. It is well known that there is a cerous-ceric equilibrium in silicate glasses under normal melting conditions. The position of this equilibrium depends on glass composition, melting temperature, furnace atmosphere, and possibly the total amounts of cerium in glass. The oxidation state of cerium affects total solubility of cerium in glass, solubilities of other components in glass, viscosities and liquidus temperatures of the melts, and the chemical durability of the glasses. A procedure was developedmore » for the determination of the ceric and cerous distribution. The glass was ground to small particles of less than 300 meshes and was dissolved in mixture of HF and H{sub 2}SO{sub 4}. The ceric oxide was graduately reduced to cerous species in the presence of HF acid during the dissolution. To compensate the change of the equilibrium during the dissolution, a calibration curve is made with a mixture of standard solution of ceric sulphate and one gram of glass of the same composition containing no cerium. Boric acid was added to complex the fluoride ions, and the resultant solution was titrated potentiometrically with 0.01 N ferrous ammonium sulphate solution. The corrected ceric concentration was obtained on the calibration curve. The total cerium content in the above solution was analyzed using ICP-AES and the cerous content was the difference between the total Ce and Ce(+4).« less

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

NASA Astrophysics Data System (ADS)

Li, Jingyi; Mao, Jingqiu; Fiore, Arlene M.; Cohen, Ronald C.; Crounse, John D.; Teng, Alex P.; Wennberg, Paul O.; Lee, Ben H.; Lopez-Hilfiker, Felipe D.; Thornton, Joel A.; Peischl, Jeff; Pollack, Ilana B.; Ryerson, Thomas B.; Veres, Patrick; Roberts, James M.; Neuman, J. Andrew; Nowak, John B.; Wolfe, Glenn M.; Hanisco, Thomas F.; Fried, Alan; Singh, Hanwant B.; Dibb, Jack; Paulot, Fabien; Horowitz, Larry W.

2018-02-01

Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July-August 2004), SENEX (June-July 2013), and SEAC4RS (August-September 2013) and long-term ground measurement networks alongside a global chemistry-climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (˜ 42-45 %), followed by NOx (31 %), total peroxy nitrates (ΣPNs; 14 %), and total alkyl nitrates (ΣANs; 9-12 %) on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.

US EPA's SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, volatile o...

EPA’s SPECIATE 4.4 Database: Bridging Data Sources and Data Users

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

pH-specific synthesis and spectroscopic, structural, and magnetic studies of a chromium(III)-citrate species. Aqueous solution speciation of the binary chromium(III)-citrate system.

PubMed

Gabriel, C; Raptopoulou, C P; Terzis, A; Tangoulis, V; Mateescu, C; Salifoglou, A

2007-04-16

In an attempt to understand the aqueous interactions of Cr(III) with the low-molecular-mass physiological ligand citric acid, the pH-specific synthesis in the binary Cr(III)-citrate system was explored, leading to the complex (NH4)4[Cr(C6H4O7)(C6H5O7)].3H2O (1). 1 crystallizes in the monoclinic space group I2/a, with a = 19.260(10) A, b = 10.006(6) A, c = 23.400(10) A, beta = 100.73(2) degrees , V = 4431(4) A3, and Z = 8. 1 was characterized by elemental analysis and spectroscopic, structural, thermal, and magnetic susceptibility studies. Detailed aqueous speciation studies in the Cr(III)-citrate system suggest the presence of a number of species, among which is the mononuclear [Cr(C6H4O7)(C6H5O7)]4- complex, optimally present around pH approximately 5.5. The structure of 1 reveals a mononuclear octahedral complex of Cr(III) with two citrate ligands bound to it. The two citrate ligands have different deprotonation states, thus signifying the importance of the mixed deprotonation state in the coordination sphere of the Cr(III) species in aqueous speciation. The latter reveals the distribution of numerous species, including 1, for which the collective structural, spectroscopic, and magnetic data point out its physicochemical profile in the solid state and in solution. The importance of the synthetic efforts linked to 1 and the potential ramifications of Cr(III) reactivity toward both low- and high-molecular-mass biotargets are discussed in light of (a) the quest for well-characterized soluble Cr(III) species that could be detected and identified in biologically relevant fluids, (b) ongoing efforts to delineate the aqueous speciation of the Cr(III)-citrate system and its link to biotoxic Cr(III) manifestations, and (c) the synthetic utility of convenient Cr(III) precursors in the synthesis of advanced materials.

Invasive species and biodiversity crises: testing the link in the late devonian.

PubMed

Stigall, Alycia L

2010-12-29

During the Late Devonian Biodiversity Crisis, the primary driver of biodiversity decline was the dramatic reduction in speciation rates, not elevated extinction rates; however, the causes of speciation decline have been previously unstudied. Speciation, the formation of new species from ancestral populations, occurs by two primary allopatric mechanisms: vicariance, where the ancestral population is passively divided into two large subpopulations that later diverge and form two daughter species, and dispersal, in which a small subset of the ancestral population actively migrates then diverges to form a new species. Studies of modern and fossil clades typically document speciation by vicariance in much higher frequencies than speciation by dispersal. To assess the mechanism behind Late Devonian speciation reduction, speciation rates were calculated within stratigraphically constrained species-level phylogenetic hypotheses for three representative clades and mode of speciation at cladogenetic events was assessed across four clades in three phyla: Arthropoda, Brachiopoda, and Mollusca. In all cases, Devonian taxa exhibited a congruent reduction in speciation rate between the Middle Devonian pre-crisis interval and the Late Devonian crisis interval. Furthermore, speciation via vicariance is almost entirely absent during the crisis interval; most episodes of speciation during this time were due to dispersal. The shutdown of speciation by vicariance during this interval was related to widespread interbasinal species invasions. The lack of Late Devonian vicariance is diametrically opposed to the pattern observed in other geologic intervals, which suggests the loss of vicariant speciation attributable to species invasions during the Late Devonian was a causal factor in the biodiversity crisis. Similarly, modern ecosystems, in which invasive species are rampant, may be expected to exhibit similar shutdown of speciation by vicariance as an outcome of the modern biodiversity crisis.

Sources, spatial variation, and speciation of heavy metals in sediments of the Tamagawa River in Central Japan.

PubMed

Shikazono, N; Tatewaki, K; Mohiuddin, K M; Nakano, T; Zakir, H M

2012-01-01

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.

Fate of Zinc Oxide Nanoparticles during Anaerobic Digestion of Wastewater and Post-Treatment Processing of Sewage Sludge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lombi, Enzo; Donner, Erica; Tavakkoli, Ehsan

2013-01-14

The rapid development and commercialization of nanomaterials will inevitably result in the release of nanoparticles (NPs) to the environment. As NPs often exhibit physical and chemical properties significantly different from those of their molecular or macrosize analogs, concern has been growing regarding their fate and toxicity in environmental compartments. The wastewater-sewage sludge pathway has been identified as a key release pathway leading to environmental exposure to NPs. In this study, we investigated the chemical transformation of two ZnO-NPs and one hydrophobic ZnO-NP commercial formulation (used in personal care products), during anaerobic digestion of wastewater. Changes in Zn speciation as amore » result of postprocessing of the sewage sludge, mimicking composting/stockpiling, were also assessed. The results indicated that 'native' Zn and Zn added either as a soluble salt or as NPs was rapidly converted to sulfides in all treatments. The hydrophobicity of the commercial formulation retarded the conversion of ZnO-NP. However, at the end of the anaerobic digestion process and after postprocessing of the sewage sludge (which caused a significant change in Zn speciation), the speciation of Zn was similar across all treatments. This indicates that, at least for the material tested, the risk assessment of ZnO-NP through this exposure pathway can rely on the significant knowledge already available in regard to other 'conventional' forms of Zn present in sewage sludge.« less

Mercury emissions and species during combustion of coal and waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong Yao; Guangqian Luo; Minghou Xu

2006-10-15

The behaviors of mercury evolution for three types of coal and three types of dried sewage sludge are studied using a thermogravimetric (TG) analyzer. The mercury speciations in the flue gas from coal and sludge combustion are also analyzed by implementing a horizontal electrically heated tube furnace. Furthermore, the kinetic calculations of mercury oxidizing processes are carried out using the software package CHEMKIN in order to interpret the homogeneous mechanism of mercury oxidization. The results obtained show that the sulfur content in the sludge inhibits the evolution of mercury at low temperature if the Cl concentration is high enough. Chlorinemore » enhances mercury evolution in the coal combustion, whereas there is no relationship when the Cl concentration is high. Fixed carbon content plays a role in depression of the mercury evolution. Formation of oxidized mercury (HgCl{sub 2}) does not relate to the chlorine concentration in the raw coal and sludge. Whereas the ash and sulfur content in the sludge affects the Hg oxidization, kinetic calculations show that HgCl, Cl{sub 2}, and HOCl formation is important in producing the oxidized mercury during combustion of coal and sludge at 873 K. A suitable temperature for Hg oxidization when Cl{sub 2} is the oxidization resource is 700-1200 K. 32 refs., 10 figs., 5 tabs.« less

Estimation and influence of physicochemical properties and chemical fractions of surface sediment on the bioaccessibility of Cd and Hg contaminant in Langat River, Malaysia.

PubMed

Kadhum, Safaa A; Ishak, Mohd Yusoff; Zulkifli, Syaizwan Zahmir

2017-10-01

This study applied the use of sequential extraction technique and simple bioaccessibility extraction test to quantify the bioavailable fractions and the human bioaccessible concentration of metals collected from nine stations in surface sediment of the Langat River. The concentrations of total and bioaccessible metals from different stations were in the range of 0.49-1.04, 0.10-0.32 μg g -1 for T-Cd, Bio-Cd, respectively, and 12.9-128.03, 2.06-8.53 μg kg -1 for T-Hg, Bio-Hg, respectively. The results revealed highest R-Bio-Cd in Banting station (55.3 %), while the highest R-Bio-Hg was in Kajang station (49.61 %). The chemical speciation of Cd in most sampling stations was in the order of oxidisable-organic > residual > exchangeable > acid-reducible, while speciation of Hg was in the order of exchangeable > residual > oxidisable-organic > acid-reducible. The correlation matric of mean content showed that the TOM, particle size and Mg ++ in polluted surface sediments was highly correlated with total mercury. The PCA showed that the main factors influencing the bioaccessibility of Hg in surface sediments were the sediment TOM, F1 (EFLE) and F3 (oxidation-organic), while the factor influencing the bioaccessibility of Cd was the F3 (oxidation-organic) and T-Cd.

Mercury (II) reduction and co-precipitation of metallic mercury on hydrous ferric oxide in contaminated groundwater.

PubMed

Richard, Jan-Helge; Bischoff, Cornelia; Ahrens, Christian G M; Biester, Harald

2016-01-01

Mercury (Hg) speciation and sorption analyses in contaminated aquifers are useful for understanding transformation, retention, and mobility of Hg in groundwater. In most aquifers hydrous ferric oxides (HFOs) are among the most important sorbents for trace metals; however, their role in sorption or mobilization of Hg in aquifers has been rarely analyzed. In this study, we investigated Hg chemistry and Hg sorption to HFO under changing redox conditions in a highly HgCl2-contaminated aquifer (up to 870μgL(-1) Hg). Results from aqueous and solid phase Hg measurements were compared to modeled (PHREEQC) data. Speciation analyses of dissolved mercury indicated that Hg(II) forms were reduced to Hg(0) under anoxic conditions, and adsorbed to or co-precipitated with HFO. Solid phase Hg thermo-desorption measurements revealed that between 55 and 93% of Hg bound to HFO was elemental Hg (Hg(0)). Hg concentrations in precipitates reached more than 4 weight %, up to 7000 times higher than predicted by geochemical models that do not consider unspecific sorption to and co-precipitation of elemental Hg with HFO. The observed process of Hg(II) reduction and Hg(0) formation, and its retention and co-precipitation by HFO is thought to be crucial in HgCl2-contaminated aquifers with variable redox-conditions regarding the related decrease in Hg solubility (factor of ~10(6)), and retention of Hg in the aquifer. Copyright © 2015 Elsevier B.V. All rights reserved.

Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

2016-05-01

This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds.

Influence of the hydration by the environmental humidity on the metallic speciation and the photocatalytic activity of Cr/MCM-41

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elías, Verónica R.; Sabre, Ema V.; Winkler, Elin L.

2014-05-01

The influence of the environmental humidity on the Cr species deposited on inorganic supports like MCM-41 silicates was analyzed by UV–vis Diffuse Reflectance (UV–vis RD), Electronic Spin Resonance (ESR) and X-ray near-edge (XANES) spectroscopy. Metal speciation could be inferred, finding that prolonged exposure periods under environmental humidity provoked the reduction of the active Cr{sup 6+} species and thus, the decrease of the Cr/MCM-41 photoactivity. After the Ti loading over the Cr modified samples, Cr species and the photoactivity were not notably influenced by the humidity exposure. Thus, it could be concluded that the presence of Ti is important because themore » TiO{sub 2} cover protects the oxidized Cr species, stabilizing them. - Graphical abstract: The load of Ti on the Cr modified MCM-41 produces a TiO{sub 2} cover that protects the active Cr species from their reduction by the environmental humidity. - Highlights: • Spectroscopic analysis shows presence of Cr{sup 6+}/Cr{sup 5+} in calcined/re-calcined samples. • Cr{sup 3+} species increase for hydrated samples causing their photoactivity decrease. • Samples with high Cr loadings are more sensitive to environmental humidity presence. • TiO{sub 2} cover protects oxidized Cr species from their reduction by the water. • Ti is important to allow a synergistic effect and to stabilize active Cr{sup 6+}/Cr{sup 5+}.« less

Charge distribution and local structure and speciation in the UO 2+x and PuO 2+x binary oxides for x⩽0.25

NASA Astrophysics Data System (ADS)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Webster Keogh, D.; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Drew Tait, C.; Kirk Veirs, D.; Villella, Phillip M.; Wastin, Franck

2005-02-01

The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO 2+x (0.00⩽ x⩽0.20) and PuO 2+x/PuO 2+x-y(OH) 2y· zH 2O have been determined by U/Pu L III XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75 Å) U-O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO 2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO 2+x system, which does not show a separate phase at its x=0.25 endpoint, also displays (1) oxo groups at longer 1.9 Å distances consistent with Pu(V+ δ), (2) a multisite Pu-O distribution even when x is close to zero indicative of the formation of stable species with H 2O and its hydrolysis products with O 2-, and (3) a highly disordered, spectroscopically invisible Pu-Pu component. The structure and bonding in AnO 2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements.

Arsenite oxidation by the phyllosphere bacterial community associated with Wolffia australiana.

PubMed

Xie, Wan-Ying; Su, Jian-Qiang; Zhu, Yong-Guan

2014-08-19

Speciation is a key determinant in the toxicity, behavior, and fate of arsenic (As) in the environment. However, little is known about the transformation of As species mediated by floating macrophytes and the phyllosphere bacteria in aquatic and wetland environment. In this study, Wolffia australiana, a rootless floating duckweed, was cultured with (W+B) or without (W-B) phyllosphere bacteria to investigate its ability in arsenite (As(III)) oxidation. Results showed that sterile W. australiana did not oxidize As(III) in the growth medium or in plant tissue, whereas W. australiana with phyllpsphere bacteria displayed substantial As(III) oxidation in the medium. Quantitative PCR of As redox-related functional genes revealed the dominance of the arsenite oxidase (aioA) gene in the phyllosphere bacterial community. These results demonstrate that the phyllosphere bacteria were responsible for the As(III) oxidation in the W+B system. The rapid oxidation of As(III) by the phyllosphere bacterial community may suppress As accumulation in plant tissues under phosphate rich conditions. The aioA gene library showed that the majority of the phyllosphere arsenite-oxidizing bacteria related either closely to unidentified bacteria found in paddy environments or distantly to known arsenite-oxidizing bacteria. Our research suggests a previously overlooked diversity of arsenite-oxidizing bacteria in the phyllosphere of aquatic macrophytes which may have a substantial impact on As biogeochemistry in water environments, warranting further exploration.

Non-equilibrium dynamics and floral trait interactions shape extant angiosperm diversity

PubMed Central

O'Meara, Brian C.; Smith, Stacey D.; Armbruster, W. Scott; Harder, Lawrence D.; Hardy, Christopher R.; Hileman, Lena C.; Hufford, Larry; Litt, Amy; Magallón, Susana; Smith, Stephen A.; Stevens, Peter F.; Fenster, Charles B.; Diggle, Pamela K.

2016-01-01

Why are some traits and trait combinations exceptionally common across the tree of life, whereas others are vanishingly rare? The distribution of trait diversity across a clade at any time depends on the ancestral state of the clade, the rate at which new phenotypes evolve, the differences in speciation and extinction rates across lineages, and whether an equilibrium has been reached. Here we examine the role of transition rates, differential diversification (speciation minus extinction) and non-equilibrium dynamics on the evolutionary history of angiosperms, a clade well known for the abundance of some trait combinations and the rarity of others. Our analysis reveals that three character states (corolla present, bilateral symmetry, reduced stamen number) act synergistically as a key innovation, doubling diversification rates for lineages in which this combination occurs. However, this combination is currently less common than predicted at equilibrium because the individual characters evolve infrequently. Simulations suggest that angiosperms will remain far from the equilibrium frequencies of character states well into the future. Such non-equilibrium dynamics may be common when major innovations evolve rarely, allowing lineages with ancestral forms to persist, and even outnumber those with diversification-enhancing states, for tens of millions of years. PMID:27147092

Non-equilibrium dynamics and floral trait interactions shape extant angiosperm diversity.

PubMed

O'Meara, Brian C; Smith, Stacey D; Armbruster, W Scott; Harder, Lawrence D; Hardy, Christopher R; Hileman, Lena C; Hufford, Larry; Litt, Amy; Magallón, Susana; Smith, Stephen A; Stevens, Peter F; Fenster, Charles B; Diggle, Pamela K

2016-05-11

Why are some traits and trait combinations exceptionally common across the tree of life, whereas others are vanishingly rare? The distribution of trait diversity across a clade at any time depends on the ancestral state of the clade, the rate at which new phenotypes evolve, the differences in speciation and extinction rates across lineages, and whether an equilibrium has been reached. Here we examine the role of transition rates, differential diversification (speciation minus extinction) and non-equilibrium dynamics on the evolutionary history of angiosperms, a clade well known for the abundance of some trait combinations and the rarity of others. Our analysis reveals that three character states (corolla present, bilateral symmetry, reduced stamen number) act synergistically as a key innovation, doubling diversification rates for lineages in which this combination occurs. However, this combination is currently less common than predicted at equilibrium because the individual characters evolve infrequently. Simulations suggest that angiosperms will remain far from the equilibrium frequencies of character states well into the future. Such non-equilibrium dynamics may be common when major innovations evolve rarely, allowing lineages with ancestral forms to persist, and even outnumber those with diversification-enhancing states, for tens of millions of years. © 2016 The Author(s).

Recent Advances in the Measurement of Arsenic, Cadmium, and Mercury in Rice and Other Foods

PubMed Central

Punshon, Tracy

2015-01-01

Trace element analysis of foods is of increasing importance because of raised consumer awareness and the need to evaluate and establish regulatory guidelines for toxic trace metals and metalloids. This paper reviews recent advances in the analysis of trace elements in food, including challenges, state-of-the art methods, and use of spatially resolved techniques for localizing the distribution of As and Hg within rice grains. Total elemental analysis of foods is relatively well-established but the push for ever lower detection limits requires that methods be robust from potential matrix interferences which can be particularly severe for food. Inductively coupled plasma mass spectrometry (ICP-MS) is the method of choice, allowing for multi-element and highly sensitive analyses. For arsenic, speciation analysis is necessary because the inorganic forms are more likely to be subject to regulatory limits. Chromatographic techniques coupled to ICP-MS are most often used for arsenic speciation and a range of methods now exist for a variety of different arsenic species in different food matrices. Speciation and spatial analysis of foods, especially rice, can also be achieved with synchrotron techniques. Sensitive analytical techniques and methodological advances provide robust methods for the assessment of several metals in animal and plant-based foods, in particular for arsenic, cadmium and mercury in rice and arsenic speciation in foodstuffs. PMID:25938012

Loss of sexual recombination and segregation is associated with increased diversification in evening primroses.

PubMed

Johnson, Marc T J; Fitzjohn, Richard G; Smith, Stacey D; Rausher, Mark D; Otto, Sarah P

2011-11-01

The loss of sexual recombination and segregation in asexual organisms has been portrayed as an irreversible process that commits asexually reproducing lineages to reduced diversification. We test this hypothesis by estimating rates of speciation, extinction, and transition between sexuality and functional asexuality in the evening primroses. Specifically, we estimate these rates using the recently developed BiSSE (Binary State Speciation and Extinction) phylogenetic comparative method, which employs maximum likelihood and Bayesian techniques. We infer that net diversification rates (speciation minus extinction) in functionally asexual evening primrose lineages are roughly eight times faster than diversification rates in sexual lineages, largely due to higher speciation rates in asexual lineages. We further reject the hypothesis that a loss of recombination and segregation is irreversible because the transition rate from functional asexuality to sexuality is significantly greater than zero and in fact exceeded the reverse rate. These results provide the first empirical evidence in support of the alternative theoretical prediction that asexual populations should instead diversify more rapidly than sexual populations because they are free from the homogenizing effects of sexual recombination and segregation. Although asexual reproduction may often constrain adaptive evolution, our results show that the loss of recombination and segregation need not be an evolutionary dead end in terms of diversification of lineages. © 2011 The Author(s). Evolution© 2011 The Society for the Study of Evolution.

Microcolumn-based speciation analysis of thallium in soil and green cabbage.

PubMed

Jia, Yanlong; Xiao, Tangfu; Sun, Jialong; Yang, Fei; Baveye, Philippe C

2018-07-15

Thallium (Tl) is a toxic trace metal, whose geochemical behavior and biological effects are closely controlled by its chemical speciation in the environment. However, little tends to be known about this speciation of Tl in soil and plant systems that directly affect the safety of food supplies. In this context, the objective of the present study was to elaborate an efficient method to separate and detect Tl(I) and Tl(III) species for soil and plant samples. This method involves the selective adsorption of Tl(I) on microcolumns filled with immobilized oxine, in the presence of DTPA (diethylenetriaminepentaacetic acid), followed by DTPA-enhanced ultrasonic and heating-induced extraction, coupled with ICP-MS detection. The method was characterized by a LOD of 0.037 μg/L for Tl(I) and 0.18 μg/L for Tl(III) in 10  mL samples. With this method, a second objective of the research was to assess the speciation of Tl in pot and field soils and in green cabbage crops. Experimental results suggest that DTPA extracted Tl was mainly present as Tl(I) in soils (>95%). Tl in hyperaccumulator plant green cabbage was also mainly present as Tl(I) (>90%). With respect to Tl uptake in plants, this study provides direct evidence that green cabbage mainly takes up Tl(I) from soil, and transports it into the aboveground organs. In soils, Tl(III) is reduced to Tl(I) even at the surface where the chemical environment promotes oxidation. This observation is conducive to understanding the mechanisms of Tl isotope fractionation in the soil-plant system. Based on geochemical fraction studies, the reducible fraction was the main source of Tl getting accumulated by plants. These results indicate that the improved analytical method presented in this study offers an economical, simple, fast, and sensitive approach for the separation of Tl species present in soils at trace levels. Copyright © 2018 Elsevier B.V. All rights reserved.

Arsenic Speciation in Groundwater: Role of Thioanions

EPA Science Inventory

The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

Analysis of Halogen-Mercury Reactions in Flue Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paula Buitrago; Geoffrey Silcox; Constance Senior

2010-01-01

Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using amore » wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.« less

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; McCleskey, R. Blaine; Schoonen, Martin A.A.; Xu, Yong

2001-01-01

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

Water-chemistry and on-site sulfur-speciation data for selected springs in Yellowstone National Park, Wyoming, 1994-1995

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; Cunningham, Kirk M.; Schoonen, Martin A.; Xu, Yong; DeMonge, Jennifer M.

1998-01-01

Forty-two water analyses are reported for samples collected at 8 hot springs and their overflow drainages, two geysers, and two ambient-temperature acid streams in Yellowstone National Park during 1994-95. These water samples were collected and analyzed as part of the initial research investigations on sulfur redox speciation in the hot springs of Yellowstone and to document chemical changes in overflows that affect major ions, redox species, and trace elements. The sulfur redox speciation research is a collaboration between the State University of New York (SUNY) at Stony Brook and the U.S. Geological Survey (USGS). Four hot springs, Ojo Caliente, Azure, Frying Pan, and Angel Terrace, were studied in detail. Analyses were performed adjacent to the sampling site or in an on-site mobile lab truck constructed by the USGS, or later in a USGS laboratory. Water temperature, specific conductance, pH, Eh, D.O., and dissolved H2S were determined adjacent to the sample source at the time of sampling. Alkalinity and F- were determined on-site on the day of sample collection. Thiosulfate and polythionates were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Other major anions (Cl-, SO4 2-, Br-) also were determined on-site by IC within two days of sample collection. Ammonium, Fe(II), and Fe(total) were determined on-site by ultraviolet/visible spectrophotometry within two days of sample collection. Later in the USGS laboratory, densities were determined. Concentrations of Ca, Mg, Li, Na, and K were determined by flame atomic absorption and emission (Na, K) spectrometry. Concentrations of Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Mg, Mn, Na, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Al and Mg were determined by Zeeman-corrected graphite furnace atomic absorption spectrometry. Three important conclusions from the sampling and analyses are: (1) variability in H2S concentrations can be caused as much by sampling and preservation artifacts as by actual variations in water composition over time, (2) historical determinations of S2O3 2- were subject to overestimation, most likely because of inadequate preservation leading to H2S oxidation, and (3) S2O3 2- is a common constituent of hot spring waters.

Bats (Chiroptera: Noctilionoidea) Challenge a Recent Origin of Extant Neotropical Diversity.

PubMed

Rojas, Danny; Warsi, Omar M; Dávalos, Liliana M

2016-05-01

The mechanisms underlying the high extant biodiversity in the Neotropics have been controversial since the 19th century. Support for the influence of period-specific changes on diversification often rests on detecting more speciation events during a particular period. The timing of speciation events may reflect the influence of incomplete taxon sampling, protracted speciation, and null processes of lineage accumulation. Here we assess the influence of these factors on the timing of speciation with new multilocus data for New World noctilionoid bats (Chiroptera: Noctilionoidea). Biogeographic analyses revealed the importance of the Neotropics in noctilionoid diversification, and the critical role of dispersal. We detected no shift in speciation rate associated with the Quaternary or pre-Quaternary periods, and instead found an increase in speciation linked to the evolution of the subfamily Stenodermatinae (∼18 Ma). Simulations modeling constant speciation and extinction rates for the phylogeny systematically showed more speciation events in the Quaternary. Since recording more divergence events in the Quaternary can result from lineage accumulation, the age of extant sister species cannot be interpreted as supporting higher speciation rates during this period. Instead, analyzing the factors that influence speciation requires modeling lineage-specific traits and environmental, spatial, and ecological drivers of speciation. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

Transport, speciation, toxicity, and treatability of highway stormwater discharged to receiving waters in Louisiana : [tech summary].

DOT National Transportation Integrated Search

2013-01-01

As centralized wastewater treatment continues to improve while increasingly replacing decentralized systems, urban : rainfall-runoff has become the leading contributor of water body impairments in the United States (USEPA, 1996). For : many water bod...

In-Situ Analysis Of Metal(loid)s In Plants: State Of The Art And Artefacts

EPA Science Inventory

Metals and metalloids play important roles in plant function and metabolism. Likewise, plants subsequently introduce vital dietary nutrition to people and animals. Understanding the transport, localisation and speciation of these elements is critical for understanding availabil...

Structural, luminescence, thermodynamic and theoretical studies on mononuclear complexes of Eu(III) with pyridine monocarboxylate-N-oxides in aqueous solution

NASA Astrophysics Data System (ADS)

Dumpala, Rama Mohana Rao; Rawat, Neetika; Boda, Anil; Ali, Sk. Musharaf; Tomar, B. S.

2018-02-01

The mononuclear complexes formed by Eu(III) with three isomeric pyridine monocarboxylate-N-oxides namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO) in aqueous solutions were studied by potentiometry, luminescence spectroscopy and isothermal titration calorimetry (ITC) to determine the speciation, coordination, luminescence properties and thermodynamic parameters of the complexes formed during the course of the reaction. More stable six membered chelate complexes with stoichiometry (MLi, i = 1-4) are formed by Eu(III) with PANO while non chelating ML and ML2 complexes are formed by NANO and IANO. The stability of Eu(III) complexes follow the order PANO > IANO > NANO. The ITC studies inferred an endothermic and innersphere complex formation of Eu(III)-PANO and Eu(III)-IANO whereas an exothermic and outer-sphere complex formation for Eu(III)-NANO. The luminescence life time data further supported the ITC results. Density functional theoretical calculations were carried out to optimize geometries of the complexes and to estimate the energies, structural parameters (bond distances, bond angles) and charges on individual atoms of the same. Theoretical approximations are found to be in good agreement with the experimental observations.

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

USGS Publications Warehouse

Balistrieri, L.S.; Blank, R.G.

2008-01-01

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

Phytoavailability and geospeciation of cadmium in contaminated soil remediated by Rhodobacter sphaeroides.

PubMed

Fan, Wenhong; Jia, Yingying; Li, Xiaomin; Jiang, Wei; Lu, Lin

2012-07-01

A microorganism was isolated from oil field injection water and identified as Rhodobacter sphaeroides. It was used for the remediation of simulated cadmium-contaminated soil. The phytoavailability of Cd was investigated through wheat seedling method to determine the efficiency of remediation. It was found that after remediation, the accumulation of Cd in wheat roots and leaves decreased by 67% and 53%, respectively. The Cd speciation in soil was determined with Tessier extraction procedure. It was found that the total Cd content in soil did not change during the experiments, but the geo-speciation of Cd changed remarkably. Among the five fractions, the concentration of exchangeable phases decreased by 27-46% and that of the phases bound to Fe-Mn oxides increased by 22-44%. The decrease of Cd accumulation in wheat showed significant positive correlation with the decrease of exchangeable phases. It could be concluded that the remediation of R. sphaeroides was carried out through the conversion of Cd to more stable forms. The decrease of sulfate concentration in supernatant indicated that the R. sphaeroides consumed sulfate. Copyright © 2012 Elsevier Ltd. All rights reserved.

Investigation of lead bioimmobilization and transformation by Penicillium oxalicum SL2.

PubMed

Ye, Binhui; Luo, Yating; He, Junyu; Sun, Lijuan; Long, Bibo; Liu, Qinglin; Yuan, Xiaofeng; Dai, Peibin; Shi, Jiyan

2018-05-18

Fungi Penicillium oxalicum SL2 was applied for Pb 2+ bioremediation in aqueous solution in this study. After 7 days of incubation at different initial concentrations of Pb 2+ (0, 100, 500 and 2500 mg L -1 ), most of Pb 2+ were removed (90, 98.3, and 86.2%), the maximum Pb content in mycelium reached about 155.6 mg g -1  dw. Meanwhile, the formation of extracellular secondary minerals and intracellular Pb-complex were observed and identified, the speciation of Pb in mycelium was also detected by X-ray absorption near-edge structure (XANES) spectroscopy, i.e., Pb-oxalate, Pb-citrate, Pb-hydrogen phosphate and Pb-glutathione analogues. In addition, content of glutathione and oxidized glutathione was increased under the exposure of Pb 2+ , which implied that glutathione might play a key role in Pb immobilization and detoxification in P. oxalicum SL2. This study elucidated partial mechanisms of Pb immobilization and speciation transformation of this strain, providing an alternative biomaterial in the bioremediation of Pb-contaminated wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Coupled high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry for inorganic and organic arsenic speciation in fish tissue.

PubMed

Villa-Lojo, M C; Alonso-Rodríguez, E; López-Mahía, P; Muniategui-Lorenzo, S; Prada-Rodríguez, D

2002-06-10

A high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry (HPLC-MW-HG-AAS) coupled method is described for As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) determination. A Hamilton PRP-X100 anion-exchange column is used for carrying out the arsenic species separation. As mobile phase 17 mM phosphate buffer (pH 6.0) is used for As(III), As(V), MMA and DMA separation, and ultrapure water (pH 6.0) for AsB and AsC separation. Prior to injection into the HPLC system AsB and AsC are isolated from the other arsenic species using a Waters Accell Plus QMA cartridge. A microwave digestion with K(2)S(2)O(8) as oxidizing agent is used for enhancing the efficiency of conversion of AsB and AsC into arsenate. Detection limits achieved were between 0.3 and 1.1 ng for all species. The method was applied to arsenic speciation in fish samples.

Experimental determination of the speciation, partitioning, and release of perrhenate as a chemical surrogate for pertechnetate from a sodalite-bearing multiphase ceramic waste form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Eric M.; Lukens, Wayne W.; Fitts, Jeff. P.

2013-12-01

A key component to closing the nuclear fuel cycle is the storage and disposition of nuclear waste in geologic systems. Multiphase ceramic waste forms have been studied extensively as a potential host matrix for nuclear waste. Understanding the speciation, partitioning, and release behavior of radionuclides immobilized in multiphase ceramic waste forms is a critical aspect of developing the scientific and technical basis for nuclear waste management. In this study, we evaluated a sodalite-bearing multiphase ceramic waste form (i.e., fluidized-bed steam reform sodium aluminosilicate [FBSR NAS] product) as a potential host matrix for long-lived radionuclides, such as technetium (99Tc). The FBSRmore » NAS material consists primarily of nepheline (ideally NaAlSiO4), anion-bearing sodalites (ideally M8[Al6Si6O24]X2, where M refers to alkali and alkaline earth cations and X refers to monovalent anions), and nosean (ideally Na8[AlSiO4]6SO4). Bulk X-ray absorption fine structure analysis of the multiphase ceramic waste form, suggest rhenium (Re) is in the Re(VII) oxidation state and has partitioned to a Re-bearing sodalite phase (most likely a perrhenate sodalite Na8[Al6Si6O24](ReO4)2). Rhenium was added as a chemical surrogate for 99Tc during the FBSR NAS synthesis process. The weathering behavior of the FBSR NAS material was evaluated under hydraulically unsaturated conditions with deionized water at 90 ?C. The steady-state Al, Na, and Si concentrations suggests the weathering mechanisms are consistent with what has been observed for other aluminosilicate minerals and include a combination of ion exchange, network hydrolysis, and the formation of an enriched-silica surface layer or phase. The steady-state S and Re concentrations are within an order of magnitude of the nosean and perrhenate sodalite solubility, respectively. The order of magnitude difference between the observed and predicted concentration for Re and S may be associated with the fact that the anion-bearing sodalites contained in the multiphase ceramic matrix are present as mixed-anion sodalite phases. These results suggest the multiphase FBSR NAS material may be a viable host matrix for long-lived, highly mobilie radionuclides which is a critical aspect in the management of nuclear waste.« less

Sulfonates: A novel class of organic sulfur compounds in marine sediments

NASA Astrophysics Data System (ADS)

Vairavamurthy, Appathurai; Zhou, Weiqing; Eglinton, Timothy; Manowitz, Bernard

1994-11-01

X-ray absorption near-edge structure spectroscopy (XANES) used to measure sulfur speciation in a variety of organic-rich marine sediments has established sulfonates as a novel and major component of sedimentary organic sulfur. The origins of sulfonates in sediments are not clear, although both biological and geochemical mechanisms are possible. The accumulation of oxidized sulfonate sulfur in reducing marine sediments was not known previously; hence, a new perspective in sulfur geochemistry is established. The biogeochemical implications of the presence of sulfonates in marine sediments are discussed.

EPAs SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of source category-specific particulate matter (PM), volatile organic gas, and other gas speciation profiles of air pollutant emissions. Abt Associates, Inc. developed SPECIATE 4.4 through a collaborat...

SPECIATE Version 4.4 Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for regi...

SPECIATE - EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of total organic compound (TOC) and particulate matter (PM) speciation profiles for emissions from air pollution sources. The data base has recently been updated and an associated report has recently been re...

Speciation has a spatial scale that depends on levels of gene flow.

PubMed

Kisel, Yael; Barraclough, Timothy G

2010-03-01

Area is generally assumed to affect speciation rates, but work on the spatial context of speciation has focused mostly on patterns of range overlap between emerging species rather than on questions of geographical scale. A variety of geographical theories of speciation predict that the probability of speciation occurring within a given region should (1) increase with the size of the region and (2) increase as the spatial extent of intraspecific gene flow becomes smaller. Using a survey of speciation events on isolated oceanic islands for a broad range of taxa, we find evidence for both predictions. The probability of in situ speciation scales with island area in bats, carnivorous mammals, birds, flowering plants, lizards, butterflies and moths, and snails. Ferns are an exception to these findings, but they exhibit high frequencies of polyploid and hybrid speciation, which are expected to be scale independent. Furthermore, the minimum island size for speciation correlates across groups with the strength of intraspecific gene flow, as is estimated from a meta-analysis of published population genetic studies. These results indicate a general geographical model of speciation rates that are dependent on both area and gene flow. The spatial scale of population divergence is an important but neglected determinant of broad-scale diversity patterns.

The darkening of zinc yellow: XANES speciation of chromium in artist;s paints after light and chemical exposures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zanella, Luciana; Casadio, Francesca; Gray, Kimberly A.

2012-03-14

The color darkening of selected brushstrokes of the masterpiece A Sunday on La Grande Jatte - 1884 (by Georges Seurat) has been attributed to the alteration of the chromate pigment zinc yellow. The pigment originally displays a bright greenish-yellow color but may undergo, after aging, darkening to a dull, ocher tone. We used XANES to probe the oxidation state of Cr on paint reconstructions, and show that color changes are associated with the reduction of Cr(VI) to Cr(III). Paint mixtures containing the pigment and linseed oil to mimic mixtures used in La Grande Jatte were subjected to artificial aging inmore » the presence of light, SO{sub 2}, and variable air humidity - 50 and 90% relative humidity. High relative humidity led to the largest degree of Cr(VI) reduction whereas low relative humidity promoted light-induced alterations. These results are corroborated by visible reflectance measurements on the same laboratory samples and contribute to a better understanding of the chemical reactivity of chromate pigments, which are present in many historical works of art.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timonen, Hilkka; Cubison, Mike; Aurela, Minna

The applicability, methods and limitations of constrained peak fitting on mass spectra of low mass resolving power ( m/Δ m 50~500) recorded with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) are explored. Calibration measurements as well as ambient data are used to exemplify the methods that should be applied to maximise data quality and assess confidence in peak-fitting results. Sensitivity analyses and basic peak fit metrics such as normalised ion separation are employed to demonstrate which peak-fitting analyses commonly performed in high-resolution aerosol mass spectrometry are appropriate to perform on spectra of this resolving power. Information on aerosol sulfate, nitrate,more » sodium chloride, methanesulfonic acid as well as semi-volatile metal species retrieved from these methods is evaluated. The constants in a commonly used formula for the estimation of the mass concentration of hydrocarbon-like organic aerosol may be refined based on peak-fitting results. Lastly, application of a recently published parameterisation for the estimation of carbon oxidation state to ToF-ACSM spectra is validated for a range of organic standards and its use demonstrated for ambient urban data.« less

The Incredible Diversity of Fe-bearing Phases at Gusev Crater, Mars, According to the Mars Exploration Rover Moessbauer Spectrometer

NASA Technical Reports Server (NTRS)

Morris, R. V.; Klingelhoefer, G.; Schroeder, C.; Rodionov, D. S.; Ming, D. W.; Yen, A.

2006-01-01

The Mars Exploration Rover (MER) Spirit landed on the plains of Gusev Crater on 4 January 2004. One primary scientific objective for the mission is to characterize the mineralogical and elemental composition of surface materials, searching for evidence of water and clues for assessing past and current climates and their suitability for life [1]. The role of the Moessbauer (MB) spectrometer on Spirit is to provide quantitative information about the distribution of Fe among its oxidation and coordination states, identification of Fe-bearing phases, and relative distribution of Fe among those phases. The speciation and distribution of Fe in Martian rock and soil constrains the primary rock types, redox conditions under which primary minerals crystallized, the extent of alteration and weathering, the type of alteration and weathering products, and the processes and environmental conditions for alteration and weathering. In this abstract, we discuss the incredible diversity of Fe-bearing phases detected by Spirit s MB instrument during its first 540 sols of exploration at Gusev crater [2,3].

Absorption spectroscopic studies of Np(IV) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, D. T.

2004-01-01

The complexation of neptunium (IV) with selected inorganic and organic ligands was studied as part of an investigation to establish key subsurface interactions between neptunium and biological systems. The prevalence of reducing environments in most subsurface migation scenarios, which are in many cases induced by biological activity, has increased the role and importance of Np(IV) as a key subsurface neptunium oxidation state. The biodegradation of larger organics that often coexist with actinides in the subsurface leads to the formation of many organic acids as transient products that, by complexation, play a key role in defining the fate and speciation ofmore » neptunium in biologically active systems. These often compete with inorganic complexes e.g. hydrolysis and phosphate. Herein we report the results of a series of complexation studies based on new band formation of the characteristic 960 nm band for Np(IV). Formation constants for Np(IV) complexes with phosphate, hydrolysis, succinate, acetohydroxamic acid, and acetate were determined. These results show the 960 nm absorption band to be very amenable to these types of complexation studies.« less

Arsenic contamination of groundwater: a review of sources, prevalence, health risks, and strategies for mitigation.

PubMed

Shankar, Shiv; Shanker, Uma; Shikha

2014-01-01

Arsenic contamination of groundwater in different parts of the world is an outcome of natural and/or anthropogenic sources, leading to adverse effects on human health and ecosystem. Millions of people from different countries are heavily dependent on groundwater containing elevated level of As for drinking purposes. As contamination of groundwater, poses a serious risk to human health. Excessive and prolonged exposure of inorganic As with drinking water is causing arsenicosis, a deteriorating and disabling disease characterized by skin lesions and pigmentation of the skin, patches on palm of the hands and soles of the feet. Arsenic poisoning culminates into potentially fatal diseases like skin and internal cancers. This paper reviews sources, speciation, and mobility of As and global overview of groundwater As contamination. The paper also critically reviews the As led human health risks, its uptake, metabolism, and toxicity mechanisms. The paper provides an overview of the state-of-the-art knowledge on the alternative As free drinking water and various technologies (oxidation, coagulation flocculation, adsorption, and microbial) for mitigation of the problem of As contamination of groundwater.

Selected heavy metals speciation in chemically stabilised sewage sludge

NASA Astrophysics Data System (ADS)

Wiśniowska, Ewa; Włodarczyk-Makuła, Marła

2017-11-01

Selected heavy metals (Pb, Ni, Cd) were analysed in soil, digested sewage sludge as well as in the sludge stabilised with CaO or Fenton's reagent. The dose of Fenton's reagent was as follows: Fe2+ = 1g.L-1, Fe2+/H2O2=1:100; stabilisation lasted for 2 h. Dose of CaO was equal to 1 g CaO.g d.m.-1 Total concentration of all metals in the digested sewage sludge was higher than in the soil. Chemical stabilisation of sludge with Fenton's reagent increased total metal content in the sludge as a result of total solids removal. Opposite effect was stated when the sludge was mixed with CaO. Also chemical fractions of heavy metals were identified (exchangeable, carbonate bound, iron oxides bound, organic and residual). The results indicate that stabilisation of the sludge with Fenton's reagent increased mobility of heavy metals compared to the digested sludge. Amendment of CaO increased percent share of examined metals in residual fraction, thus immobilised them and decreased their bioavailability.

Arsenic Contamination of Groundwater: A Review of Sources, Prevalence, Health Risks, and Strategies for Mitigation

PubMed Central

Shikha

2014-01-01

Arsenic contamination of groundwater in different parts of the world is an outcome of natural and/or anthropogenic sources, leading to adverse effects on human health and ecosystem. Millions of people from different countries are heavily dependent on groundwater containing elevated level of As for drinking purposes. As contamination of groundwater, poses a serious risk to human health. Excessive and prolonged exposure of inorganic As with drinking water is causing arsenicosis, a deteriorating and disabling disease characterized by skin lesions and pigmentation of the skin, patches on palm of the hands and soles of the feet. Arsenic poisoning culminates into potentially fatal diseases like skin and internal cancers. This paper reviews sources, speciation, and mobility of As and global overview of groundwater As contamination. The paper also critically reviews the As led human health risks, its uptake, metabolism, and toxicity mechanisms. The paper provides an overview of the state-of-the-art knowledge on the alternative As free drinking water and various technologies (oxidation, coagulation flocculation, adsorption, and microbial) for mitigation of the problem of As contamination of groundwater. PMID:25374935

Evaluating EDGARv4.tox2 speciated mercury emissions ex-post scenarios and their impacts on modelled global and regional wet deposition patterns

NASA Astrophysics Data System (ADS)

Muntean, Marilena; Janssens-Maenhout, Greet; Song, Shaojie; Giang, Amanda; Selin, Noelle E.; Zhong, Hui; Zhao, Yu; Olivier, Jos G. J.; Guizzardi, Diego; Crippa, Monica; Schaaf, Edwin; Dentener, Frank

2018-07-01

Speciated mercury gridded emissions inventories together with chemical transport models and concentration measurements are essential when investigating both the effectiveness of mitigation measures and the mercury cycle in the environment. Since different mercury species have contrasting behaviour in the atmosphere, their proportion in anthropogenic emissions could determine the spatial impacts. In this study, the time series from 1970 to 2012 of the EDGARv4.tox2 global mercury emissions inventory are described; the total global mercury emission in 2010 is 1772 tonnes. Global grid-maps with geospatial distribution of mercury emissions at a 0.1° × 0.1° resolution are provided for each year. Compared to the previous tox1 version, tox2 provides updates for more recent years and improved emissions in particular for agricultural waste burning, power generation and artisanal and small-scale gold mining (ASGM) sectors. We have also developed three retrospective emissions scenarios based on different hypotheses related to the proportion of mercury species in the total mercury emissions for each activity sector; improvements in emissions speciation are seen when using information primarily from field measurements. We evaluated them using the GEOS-Chem 3-D mercury model in order to explore the influence of speciation shifts, to reactive mercury forms in particular, on regional wet deposition patterns. The reference scenario S1 (EDGARv4.tox2_S1) uses speciation factors from the Arctic Monitoring and Assessment Programme (AMAP); scenario S2 ("EPA_power") uses factors from EPA's Information Collection Request (ICR); and scenario S3 ("Asia_filedM") factors from recent scientific publications. In the reference scenario, the sum of reactive mercury emissions (Hg-P and Hg2+) accounted for 25.3% of the total global emissions; the regions/countries that have shares of reactive mercury emissions higher than 6% in total global reactive mercury are China+ (30.9%), India+ (12.5%) and the United States (9.9%). In 2010, the variations of reactive mercury emissions amongst the different scenarios are in the range of -19.3 t/yr (China+) to 4.4 t/yr (OECD_Europe). However, at the sector level, the variation could be different, e.g., for the iron and steel industry in China reaches 15.4 t/yr. Model evaluation at the global level shows a variation of approximately ±10% in wet deposition for the three emissions scenarios. An evaluation of the impact of mercury speciation within nested grid sensitivity simulations is performed for the United States and modelled wet deposition fluxes are compared with measurements. These studies show that using the S2 and S3 emissions of reactive mercury, can improve wet deposition estimates near sources.

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

USGS Publications Warehouse

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using extended X-ray absorption fine structure (EXAFS) and microfocused synchrotron X-ray fluorescence (μSXRF) mapping, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and microfocused EXAFS spectra of Zn in the biogenic Mn oxide coating are indicative of Zn forming triple-corner-sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to the decrease in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in the solid/solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating that desorption is not controlled by dissolution of secondary Zn phases. In summary, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process of Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Influence of the sulfur species reactivity on biofilm conformation during pyrite colonization by Acidithiobacillus thiooxidans.

PubMed

Lara, René H; García-Meza, J Viridiana; Cruz, Roel; Valdez-Pérez, Donato; González, Ignacio

2012-08-01

Massive pyrite (FeS₂) electrodes were potentiostatically modified by means of variable oxidation pulse to induce formation of diverse surface sulfur species (S(n)²⁻, S⁰). The evolution of reactivity of the resulting surfaces considers transition from passive (e.g., Fe(1-x )S₂) to active sulfur species (e.g., Fe(1-x )S(2-y ), S⁰). Selected modified pyrite surfaces were incubated with cells of sulfur-oxidizing Acidithiobacillus thiooxidans for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the attached cells density and their exopolysaccharides were analyzed by confocal laser scanning microscopy (CLMS) and atomic force microscopy (AFM) on bio-oxidized surfaces; additionally, S(n)²⁻/S⁰ speciation was carried out on bio-oxidized and abiotic pyrite surfaces using Raman spectroscopy. Our results indicate an important correlation between the evolution of S(n)²⁻/S⁰ surface species ratio and biofilm formation. Hence, pyrite surfaces with mainly passive-sulfur species were less colonized by A. thiooxidans as compared to surfaces with active sulfur species. These results provide knowledge that may contribute to establishing interfacial conditions that enhance or delay metal sulfide (MS) dissolution, as a function of the biofilm formed by sulfur-oxidizing bacteria.

Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moncur, Michael C.; Paktunc, Dogan; Jean Birks, S.

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrationsmore » in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(-I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.« less

Combining Textural Techniques to Explore Effects of Diagenesis and Low-grade Metamorphism on Iron Mineralogy and Iron Speciation

NASA Astrophysics Data System (ADS)

Slotznick, S. P.; Webb, S.; Eiler, J. M.; Kirschvink, J. L.; Fischer, W. W.

2016-12-01

Iron chemistry and mineralogy in the sedimentary rocks provide a valuable tool for studying paleoenvironmental conditions due to the fact that iron atoms can take on either the +II or +III valence state under geological redox conditions. One method utilizing this redox chemistry is `iron speciation', a bulk chemical sequential extraction technique that maps proportions of iron species to redox conditions empirically calibrated from modern sediments. However, all Precambrian and many Phanerozoic rocks have experienced post-depositional processes; it is vital to explore their effects on iron mineralogy and speciation. We combined light and electron microscopy, magnetic microscopy, (synchrotron-based) microprobe x-ray spectroscopy, and rock magnetic measurements in order to deconvolve secondary overprints from primary phases and provide quantitative measurement of iron minerals. These techniques were applied to excellently-preserved shale and siltstone samples of the 1.4 Ga lower Belt Supergroup, Montana and Idaho, USA, spanning a metamorphic gradient from sub-biotite to garnet zone. Previously measured Silurian-Devonian shales, sandstones, and carbonates in Maine and Vermont, USA spanning from the chlorite to kyanite zone provided additional well-constrained, quantitative data for comparison and to extend our analysis. In all of the studied samples, pyrrhotite formation occurred at the sub-biotite or sub-chlorite zone. Pyrrhotite was interpreted to form from pyrite and/or other iron phases based on lithology; these reactions can affect the paleoredox proxy. Iron carbonates can also severely influence iron speciation results since they often form in anoxic pore fluids during diagenesis; textural analyses of the Belt Supergroup samples highlighted that iron-bearing carbonates were early diagenetic cements or later diagenetic overprints. The inclusion of iron from diagenetic minerals during iron speciation analyses will skew results by providing a view of pore-fluid redox, not ancient water column chemistry. While our analyses and biological indicators suggest that the studied samples of the lower Belt Supergroup and New England were deposited in oxic water columns, iron speciation results imply anoxic/ferruginous conditions due to diagenetic alterations affecting the record.

SPECIATE--EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is EPA's repository of Total Organic Compound and Particulate Matter speciated profiles for a wide variety of sources. The profiles in this system are provided for air quality dispersion modeling and as a library for source-receptor and source apportionment type models. ...

SPECIATE 4.4: The Bridge Between Emissions Characterization and Modeling

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for...

Hydrological and geochemical investigations of selenium behavior at Kesterson Reservoir

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zawislanski, P.T.; Tokunaga, T.K.; Benson, S.M.

1995-05-01

This report describes research relevant to selenium specification, fractionation, physical redistribution, reduction and oxidation, and spatial distribution as related to Kesterson Reservoir. The work was carried out by scientists and engineers from the Earth Sciences Division of the Lawrence Berkeley Laboratory over a two year period from October 1992 to September 1994. Much of the focus of these efforts was on the effects of two above-average rainfall years (1991/1992 and 1992/1993). These events marked a departure from the previous six years of drought conditions, under which oxidation of Se in the soil profile led to a marked increase in solublemore » Se. Evidence from the last two years show that much of the re-oxidized Se was once more reduced due to increased soil moisture content. Also, in areas of high hydraulic conductivity, major vertical displacement of selenium and other solutes due to rainfall infiltration was observed. Such observations underscore the dependence of the future of Se speciation and distribution on environmental conditions.« less

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones

PubMed Central

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-01-01

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ66Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ66Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO42− complexes preferentially incorporate heavy δ66Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge. PMID:27982033

Combined mineralogical and EXAFS characterization of polluted sediments for the definition of technological variables and constraints

NASA Astrophysics Data System (ADS)

Brigatti, M. F.; Elmi, C.; Laurora, A.; Malferrari, D.; Medici, L.

2009-04-01

An extremely severe aspect, both from environmental and economic viewpoint, is the management of polluted sediments removed from drainage and irrigation canals. Canals, in order to retain their functionality over the time, need to have their beds, periodically cleaned from sediments there accumulating. The management of removed sediments is extremely demanding, also from an economical perspective, if these latter needs to be treated as dangerous waste materials, as stated in numerous international standards. Furthermore the disposal of such a large amount of material may introduce a significant environmental impact as well. An appealing alternative is the recovery or reuse of these materials, for example in brick and tile industry, after obviously the application of appropriate techniques and protocols that could render these latter no longer a threat for human health. The assessment of the effective potential danger for human health and ecosystem of sediments before and after treatment obviously requires both a careful chemical and mineralogical characterization and, even if not always considered in the international standards, the definition of the coordination shell of heavy metals dangerous for human health, as a function of their oxidation state and coordination (e.g. Cr and Pb), and introducing technological constraints or affecting the features of the end products. Fe is a good representative for this second category, as the features of the end product, such as color, strongly depend not only from Fe concentration but also from its oxidation state, speciation and coordination. This work will first of all provide mineralogical characterization of sediments from various sampling points of irrigation and drainage canals of Po river region in the north-eastern of Italy. Samples were investigated with various approaches including X-ray powder diffraction under non-ambient conditions, thermal analysis and EXAFS spectroscopy. Obtained results, and in particular EXAFS spectra were used to define and optimize the technological variables of the recovery process.

Immediate assessment of performance of medical laboratory scientists following a 10-day malaria microscopy training programme in Nigeria.

PubMed

Aiyenigba, Bolatito; Ojo, Abiodun; Aisiri, Adolor; Uzim, Justus; Adeusi, Oluwole; Mwenesi, Halima

2017-01-01

Rapid and precise diagnosis of malaria is an essential element in effective case management and control of malaria. Malaria microscopy is used as the gold standard for malaria diagnosis, however results remain poor as positivity rate in Nigeria is consistently over 90%. The United States President's Malaria Initiative (PMI) through the Malaria Action Program for States (MAPS) supported selected states in Nigeria to build capacity for malaria microscopy. This study demonstrates the effectiveness of in-service training on malaria microscopy amongst medical laboratory scientists. The training was based on the World Health Organization (WHO) basic microscopy training manual. The 10-day training utilized a series of didactic lectures and examination of teaching slides using a CX 21 Olympus binocular microscope. All 108 medical laboratory scientists trained from 2012 to 2015 across five states in Nigeria supported by PMI were included in the study. Evaluation of the training using a pre-and post-test method was based on written test questions; reading photographic slide images of malaria parasites; and prepared slides. There was a significant improvement in the mean written pre-and post-tests scores from 37.9% (95% CI 36.2-39.6%) to 70.7% (95% CI 68.4-73.1%) ( p  < 0.001). The mean counting post-test score improved significantly from 4.2% (95% CI 2.6-5.7%) to 27.9% (95% CI 25.3-30.5%) ( p  < 0.001). Mean post-test score for computer-based picture speciation test (63.0%) and picture detection test (89.2%) were significantly higher than the mean post-test score for slide reading speciation test (38.3%) and slide reading detection test (70.7%), p  < 0.001 in both cases. Parasite detection and speciation using enhanced visual imaging was significantly improved compared with using direct microscopy. Regular in-service training and provision of functional and high resolution microscopes are needed to ensure quality routine malaria microscopy.

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

EPA Science Inventory

Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

Heavy metals fluxes and speciation in the surface layer of urban soils in the province of Brescia (Italy)

NASA Astrophysics Data System (ADS)

Peli, Marco; Raffelli, Giulia; Barontini, Stefano; Bostick, Benjamin C.; Donna, Filippo; Lucchini, Roberto G.; Ranzi, Roberto

2017-04-01

For the last forty years (1974-2015), a ferroalloy industry has been working in Bagnolo Mella, a municipality nearby the city of Brescia (Northern Italy), producing particulate emissions enriched in heavy metals: manganese (Mn) in particular, but also lead (Pb), iron (Fe), aluminum (Al) and arsenic (As). Although some of these metals are required trace elements for most living organisms and can be largely found in natural environments (e.g. Mn being the fifth most abundant metal in the Earth crust), they all lead to toxic effects when they contaminate work and life environments of the exposed population. Aiming at contributing to quantify the exposure of the population to environmental pollution near the factory, as well as the heavy metals possible tendency to migrate through the considered soil matrix, in this work we investigated metals speciation and fluxes within the Earth Critical Zone. The factory is located near residential areas in a plain characterised by little wind and shallow water table with a great number of water resurgences. Three test sites were identified among the pronest ones to particulate matter deposition, on the basis of data collected during a previous experimental field campaign and of the local wind rose. One more site was selected upwind to the factory as a reference site minimally prone to particulate matter deposition, on the basis of the previous investigations. Sites where lawns have been maintained at least for the last forty years where selected in order to avoid agriculture—induced effects on the metals movement. Total soil metal concentrations were measured by means of a portable X-Ray Fluorescence (XRF) device along the soil profiles, down to the depth of 40 cm from the soil surface. Four loose soil samples were collected at each site, at depths ranging from 5 to 30 cm, and they were later subjected to sequential extractions procedure and ICP—MS analyses, in order to investigate differences in heavy metals speciation along the considered soil profiles. The XRF metal total content profiles show an accumulation of metals in the subsurface soil layers, around 5 cm under the soil surface (this feature is highlighted in the normalized profiles). They also give evidence of the plant activity consequences, with the closest downwind site showing values which are for all metals at least one order of magnitude -two for Mn- higher than the ones in the test site. The speciation profiles, besides describing loosely the same pattern, show how the amorphous oxides species is always prevalent for Mn and Pb along the whole profile, while for As the species associated with crystalline oxides is always the prevalent one.

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

NASA Astrophysics Data System (ADS)

Morgan, G. B., VI; Chou, I.-Ming; Pasteris, J. D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H 2C 2O 4 · 2H 2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750°C, with bulk fluid densities in the range 0.01-0.53 g/cm 3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350°C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3 H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H 2O-CO 2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of SAXENA and FEI (1988). Such disagreement suggests that the formations of CH 4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650°C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H 2O-CO 2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions.

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

USGS Publications Warehouse

Morgan, G.B.; Chou, I.-Ming; Pasteris, J.D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H2C2O4 ?? 2H2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750??C, with bulk fluid densities in the range 0.01-0.53 g/cm3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350??C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H2O-CO2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650??C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H2O-CO2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions. ?? 1992.

Speciation genetics: current status and evolving approaches

PubMed Central

Wolf, Jochen B. W.; Lindell, Johan; Backström, Niclas

2010-01-01

The view of species as entities subjected to natural selection and amenable to change put forth by Charles Darwin and Alfred Wallace laid the conceptual foundation for understanding speciation. Initially marred by a rudimental understanding of hereditary principles, evolutionists gained appreciation of the mechanistic underpinnings of speciation following the merger of Mendelian genetic principles with Darwinian evolution. Only recently have we entered an era where deciphering the molecular basis of speciation is within reach. Much focus has been devoted to the genetic basis of intrinsic postzygotic isolation in model organisms and several hybrid incompatibility genes have been successfully identified. However, concomitant with the recent technological advancements in genome analysis and a newfound interest in the role of ecology in the differentiation process, speciation genetic research is becoming increasingly open to non-model organisms. This development will expand speciation research beyond the traditional boundaries and unveil the genetic basis of speciation from manifold perspectives and at various stages of the splitting process. This review aims at providing an extensive overview of speciation genetics. Starting from key historical developments and core concepts of speciation genetics, we focus much of our attention on evolving approaches and introduce promising methodological approaches for future research venues. PMID:20439277

Ecological Speciation in Nolina parviflora (Asparagaceae): Lacking Spatial Connectivity along of the Trans-Mexican Volcanic Belt

PubMed Central

Ruiz-Sanchez, Eduardo; Specht, Chelsea D.

2014-01-01

The hypothesis of ecological speciation states that as populations diverge in different niches, reproductive isolation evolves as a by-product of adaptation to these different environments. In this context, we used Nolina parviflora as a model to test if this species evolved via ecological speciation and to explore current and historical gene flow among its populations. Nolina parviflora is a montane species endemic to Mexico with its geographical distribution restricted largely to the Trans-Mexican Volcanic Belt. This mountain range is one of the most complex geological regions in Mexico, having undergone volcanism from the mid-Miocene to the present. Ecologically, the Trans-Mexican Volcanic Belt possesses different types of vegetation, including tropical dry forest; oak, pine, pine-oak, and pine-juniper forests; and xerophytic scrub - all of which maintain populations of N. parviflora. Using species distribution models, climatic analyses, spatial connectivity and morphological comparisons, we found significant differences in climatic and morphological variables between populations of N. parviflora in two distinct Trans-Mexican Volcanic Belt regions (east vs. west). This could mean that the geographically isolated populations diverged from one another via niche divergence, indicating ecological speciation. Spatial connectivity analysis revealed no connectivity between these regions under the present or last glacial maximum climate models, indicating a lack of gene flow between the populations of the two regions. The results imply that these populations may encompass more than a single species. PMID:24905911

Mechanistic study of the influence of pyrolysis conditions on potassium speciation in biochar "preparation-application" process.

PubMed

Tan, Zhongxin; Liu, Liyun; Zhang, Limei; Huang, Qiaoyun

2017-12-01

Biochar samples produced from rice straw by pyrolysis at different temperatures (400°C and 800°C) and under different atmospheres (N 2 and CO 2 ) were applied to lettuce growth in a 'preparation-application' system. The conversion of potassium in the prepared biochar and the effect of the temperature used for pyrolysis on the bioavailability of potassium in the biochar were investigated. Root samples from lettuce plants grown with and without application of biochar were assayed by X-ray photoelectron spectroscopy (XPS). The optimal conditions for preparation of biochar to achieve the maximum bioavailability of potassium (i.e. for returning biochar to soil) were thus determined. Complex-K, a stable speciation of potassium in rice straw, was transformed into potassium sulfate, potassium nitrate, potassium nitrite, and potassium chloride after oxygen-limited pyrolysis. The aforementioned ionic-state potassium species can be directly absorbed and used by plants. Decomposition of the stable speciation of potassium during the pyrolysis process was more effective at higher temperature, whereas the pyrolysis atmosphere (CO 2 and N 2 ) had little effect on the quality of the biochar. Based on the potassium speciation in the biochar, the preparation cost, and the plant growth and rigor after the application of returning biochar to soil, 400°C and CO 2 atmosphere were the most appropriate conditions for preparation of biochar. Copyright © 2017. Published by Elsevier B.V.

Ecological speciation in Nolina parviflora (Asparagaceae): lacking spatial connectivity along of the Trans-Mexican Volcanic Belt.

PubMed

Ruiz-Sanchez, Eduardo; Specht, Chelsea D

2014-01-01

The hypothesis of ecological speciation states that as populations diverge in different niches, reproductive isolation evolves as a by-product of adaptation to these different environments. In this context, we used Nolina parviflora as a model to test if this species evolved via ecological speciation and to explore current and historical gene flow among its populations. Nolina parviflora is a montane species endemic to Mexico with its geographical distribution restricted largely to the Trans-Mexican Volcanic Belt. This mountain range is one of the most complex geological regions in Mexico, having undergone volcanism from the mid-Miocene to the present. Ecologically, the Trans-Mexican Volcanic Belt possesses different types of vegetation, including tropical dry forest; oak, pine, pine-oak, and pine-juniper forests; and xerophytic scrub--all of which maintain populations of N. parviflora. Using species distribution models, climatic analyses, spatial connectivity and morphological comparisons, we found significant differences in climatic and morphological variables between populations of N. parviflora in two distinct Trans-Mexican Volcanic Belt regions (east vs. west). This could mean that the geographically isolated populations diverged from one another via niche divergence, indicating ecological speciation. Spatial connectivity analysis revealed no connectivity between these regions under the present or last glacial maximum climate models, indicating a lack of gene flow between the populations of the two regions. The results imply that these populations may encompass more than a single species.

Assessment of Important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...