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Sample records for speciation chemical

  1. Chemical speciation of radionuclides migrating in groundwaters

    SciTech Connect

    Robertson, D.; Schilk, A.; Abel, K.; Lepel, E.; Thomas, C.; Pratt, S.; Cooper, E.; Hartwig, P.; Killey, R.

    1994-04-01

    In order to more accurately predict the rates and mechanisms of radionuclide migration from low-level waste disposal facilities via groundwater transport, ongoing studies are being conducted at field sites at Chalk River Laboratories to identify and characterize the chemical speciation of mobile, long-lived radionuclides migrating in groundwaters. Large-volume water sampling techniques are being utilized to separate and concentrate radionuclides into particular, cationic, anionic, and nonionic chemical forms. Most radionuclides are migrating as soluble, anionic species that appear to be predominantly organoradionuclide complexes. Laboratory studies utilizing anion exchange chromatography have separated several anionically complexed radionuclides, e.g., {sup 60}Co and {sup 106}Ru, into a number of specific compounds or groups of compounds. Further identification of the anionic organoradionuclide complexes is planned utilizing high resolution mass spectrometry. Large-volume ultra-filtration experiments are characterizing the particulate forms of radionuclides being transported in these groundwaters.

  2. Metal accumulation by stream bryophytes, related to chemical speciation.

    PubMed

    Tipping, E; Vincent, C D; Lawlor, A J; Lofts, S

    2008-12-01

    Metal accumulation by aquatic bryophytes was investigated using data for headwater streams of differing chemistry. The Windermere Humic Aqueous Model (WHAM) was applied to calculate chemical speciation, including competitive proton and metal interactions with external binding sites on the plants. The speciation modelling approach gives smaller deviations between observed and predicted bryophyte contents of Cu, Zn, Cd and Pb than regressions based on total filtered metal concentrations. If all four metals, and Ni, are considered together, the WHAM predictions are superior at the 1% level. Optimised constants for bryophyte binding by the trace metals are similar to those for humic substances and simple carboxylate ligands. Bryophyte contents of Na, Mg and Ca are approximately explained by binding at external sites, while most of the K is intracellular. Oxide phases account for some of the Al, and most of the Mn, Fe and Co.

  3. 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...

  4. Speciation and chemical activities in superheated sodium borate solutions

    SciTech Connect

    Weres, O. )

    1993-06-01

    The system H[sub 2]O-B[sub 2]O[sub 3]-Na[sub 2]O has been studied experimentally at 277[degrees] and 317[degrees]C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modelled using the Pitzer-Simonson Model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. These data will allow prediction of the composition and chemical behavior of sodium borate liquids that may accumulate in the superheated crevices within a steam generator. A modified form of the model is provided for use with MULTEQ. The potassium borate system also was briefly studied at 317[degrees]C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B = 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.

  5. Chemical PM2.5 Speciation in Major Cities Worldwide

    NASA Astrophysics Data System (ADS)

    Snider, Graydon; Weagle, Crystal; Brauer, Michael; Cohen, Aaron; Gibson, Mark; Liu, Yang; Martins, Vanderlei; Rudich, Yinon; Martin, Randall

    2016-04-01

    We examined the chemical composition of fine particulate matter (PM2.5) across 13 globally dispersed urban locations (including Atlanta, Buenos Aires, Beijing, Manila, and Dhaka), as part of the Surface PARTiculate mAtter Network (SPARTAN). At each site sampling was conducted over 4 to 24 months for the years 2013 to 2015. Analysis of filter samples revealed that several PM2.5 chemical components varied by more than an order of magnitude between sites. Ammonium sulfate ranged from 2 μg m-3 (Ilorin) to 17 μg m-3 (Kanpur). Ammonium nitrate ranged from 0.2 μg m-3 (Atlanta) to 6.7 μg m-3 (Kanpur). Effective black carbon ranged from 0.4 μg m-3 (Atlanta) to 5 μg m-3 (Dhaka and Kanpur). The all-site mean values of major PM2.5 constituents were ammonium sulfate (20 ± 10 %), crustal material (12 ± 6.5%), effective black carbon (10 ± 7.4 %), ammonium nitrate (3.7 ± 2.5%), sea salt (2.2 ± 1.5%), trace element oxides (0.9 ± 0.7 %), water (7.2 ± 3.0%) and residue materials (44 ± 24%). Based on the evaluation with collocated studies we treated residue material as mostly organic. Major ions generally agreed well with previous studies at the same urban locations (e.g. sulfate fractions agreed within 4% for eight out of 11 collocation comparisons). Enhanced crustal material (CM) concentrations with high Zn:Al ratios at large cities (e.g. Hanoi, Dhaka, Manila) imply significant anthropogenic CM contributions that deserve more attention. Detailed chemical speciation also aided our characterization of site-specific PM2.5 water retention. The expected water contribution to aerosols was calculated via the hygroscopicity parameter for each filter. Hourly PM2.5 at specified relative humidity (35%) was inferred from nephelometer measurements of light scatter at ambient relative humidity and 9-day filter measurements of PM2.5 mass. Our PM2.5 estimates compared favorably with a beta attenuation monitor (BAM) at the nearby US embassy in Beijing, with a coefficient of variation

  6. Mercury Speciation by X-ray Absorption Fine Structure Spectroscopy and Sequential Chemical Extractions: A Comparison of Speciation Methods

    USGS Publications Warehouse

    Kim, C.S.; Bloom, N.S.; Rytuba, J.J.; Brown, Gordon E.

    2003-01-01

    Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation-X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)-are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (> 10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O 4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.

  7. METHODS INTERCOMPARISON OF SAMPLERS FOR EPA'S NATIONAL PM 2.5 CHEMICAL SPECIATION NETWORK

    EPA Science Inventory

    The objective of this sampler intercomparison field study is to determine the performance characteristics for the collection of the chemical components of PM2.5 by the chemical speciation monitors developed for the national PM2.5 network relative to each other, to the Federal R...

  8. PM 2.5 CHEMICAL SPECIATION SAMPLER EVALUATION FIELD PROGRAM: RESULTS FROM THE FOUR CITY STUDY

    EPA Science Inventory

    The objective of this sampler intercomparison field study is to determine the performance characteristics for the collection of the chemical components of PM2.5 by the chemical speciation monitors developed for the national network relative to each other, to the Federal Referen...

  9. Effects of chemical amendments on the lability and speciation of metals in anaerobically digested biosolids.

    PubMed

    Donner, Erica; Brunetti, Gianluca; Zarcinas, Bernie; Harris, Paul; Tavakkoli, Ehsan; Naidu, Ravi; Lombi, Enzo

    2013-10-01

    The interaction of inorganic contaminants present in biosolids with iron, aluminum, and manganese oxy/hydroxides has been advocated as a key mechanism limiting their bioavailability. In this study, we investigated whether this is indeed the case, and further, whether it can be exploited to produce optimized biosolids products through the addition of chemical additives during sewage sludge processing. Experiments were conducted to investigate whether the addition of iron- and aluminum-based amendments (at 5 different rates) during the anaerobic digestion phase of wastewater treatment can effectively change the speciation or lability of contaminant metals (copper, zinc and cadmium) in biosolids destined for use in agriculture. The performance of the bioreactors was monitored throughout and the speciation and lability were determined in both fresh and 3-month aged biosolids using X-ray absorption spectroscopy (Cu, Zn) and isotopic dilution ((65)Cu, (65)Zn, (109)Cd). The tested amendments (FeCl3, Al2(SO4)3, and Al-rich water treatment residual) did not cause significant changes in metal speciation and were of limited use for reducing the lability of contaminant metals in good quality biosolids (suitable for use in agriculture), suggesting that high affinity binding sites were already in excess in these materials. However, the use of chemical amendments may offer advantages in terms of treatment process optimization and may also be beneficial when biosolids are used for contaminated site remediation. PMID:23981056

  10. Improving Molecular Level Chemical Speciation of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Worton, D. R.; Decker, M.; Isaacman, G. A.; Chan, A.; Wilson, K. R.; Goldstein, A. H.

    2013-12-01

    A substantial fraction of fine mode aerosols are organic with the majority formed in the atmosphere through oxidation of gas phase compounds emitted from a variety of natural and man-made sources. As a result, organic aerosols are comprised of thousands of individual organic species whose complexity increases exponentially with carbon number and degree of atmospheric oxidation. Chemical characterization of individual compounds present in this complex mixture provides information on sources and transformation processes that are critical for apportioning organic carbon from an often convoluted mixture of sources and to constrain oxidation mechanisms needed for atmospheric models. These compounds also affect the physical and optical properties of the aerosol but the vast majority remain unidentified and missing from published mass spectral libraries because of difficulties in separating and identifying them. We have developed improved methodologies for chemical identification in order to better understand complex environmental mixtures. Our approach has been to combine two-dimensional gas chromatography with high resolution time of flight mass spectrometry (GC×GC-HRTOFMS) and both traditional electron ionization (EI) and vacuum ultraviolet (VUV) photoionization. GC×GC provides improved separation of individual compounds over traditional one dimensional GC and minimizes co-elution of peaks resulting in mass spectra that are virtually free of interferences. VUV ionization is a ';soft' ionization technique that reduces fragmentation and enhances the abundance of the parent or molecular ion, which when combined with high resolution mass spectrometry can provide molecular formulas for chromatographic peaks. We demonstrate our methodology by applying it to identify more than 500 individual compounds in aerosol filter samples collected at Blodgett Forest, a rural site in the Sierra Nevada Mountains. Using the EI NIST mass spectral library and molecular formulas determined

  11. Partitioning of silver and chemical speciation of free Ag in soils amended with nanoparticles

    PubMed Central

    2013-01-01

    Background Knowledge about silver nanoparticles in soils is limited even if soils are a critical pathway for their environmental fate. In this paper, speciation results have been acquired using a silver ion selective electrode in three different soils. Results Soil organic matter and pH were the most important soil properties controlling the occurrence of silver ions in soils. In acidic soils, more free silver ions are available while in the presence of organic matter, ions were tightly bound in complexes. The evolution of the chemical speciation of the silver nanoparticles in soils was followed over six months. Conclusion During the first few hours, there appeared to be a strong sorption of the silver with soil ligands, whereas over time, silver ions were released, the final concentration being approximately 10 times higher than at the beginning. Ag release was associated with either the oxidation of the nanoparticles or a dissociation of adsorbed silver from the soil surfaces. PMID:23617903

  12. Chemical and physical speciation of mercury in Offatts Bayou: A seasonally anoxic bayou in Galveston Bay

    SciTech Connect

    Han, Seunghee; Lehman, Ronald D.; Choe, Key-Young; Gill, Gary A.

    2007-07-01

    A chemical equilibrium model was used to predict the solution speciation of dissolved mercury (Hg) in the stratified water column of Offatts Bayou, a subestuary in Galveston Bay, Texas, which undergoes seasonal anoxia in bottom waters. Chemical equilibrium modeling was conducted using conditional stability constants and concentrations of Hg-complexing organic ligands experimentally determined by competitive ligand equilibration methods. Dissolved Hg complexation was dominated by interactions with sulfide and dissolved organic matter (DOM) (HOHgHS0, HOHgHS(DOM), HgSHS2, and HgS 2{ 2 ) at all depths. Sulfide and glutathione competed for methylmercury (MeHg) complexation in oxic layers; in anoxic waters, sulfide complexation dominated MeHg speciation. The particle–water distribution coefficient (Kd) of Hg decreased in the anoxic layer of the water column, where the dissolved sulfide concentration increased, providing evidence that sulfide complexation influences the solubility of Hg. The solubility of MeHg was elevated in the anoxic as compared to the oxic layers, and this distributional feature was coincident with a change in the solution speciation of dissolved MeHg from glutathione/sulfide complexation in the oxic layers to a predominantly sulfide complexation in the anoxic layers. Maximum enrichment of Hg, MeHg, and iron (Fe) in suspended particulate matter was observed in the lower layer of the pycnocline, most likely resulting from formation of insoluble Fe oxide, which scavenged dissolved Hg sulfide and MeHg-sulfide species. The concomitant decrease in dissolved inorganic Hg, Fe, and sulfide in the anoxic layers is suggested to result from scavenging of inorganic Hg by FeS, which is in accordance with the Hg speciation model. Overall, Hg cycling in the water column of Offatts Bayou was associated with sulfide and DOM complexation, Fe dissolution/precipitation, water column production of MeHg, and/or efflux of MeHg from anoxic sediment.

  13. Chemical Speciation of Neptunium in Spent Fuel. 1st Progress Report

    SciTech Connect

    Czerwinski, Ken; Sherman, Christi; Reed, Don

    2000-03-02

    This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste.

  14. Chemical speciation of lead dust associated with primary lead smelting.

    PubMed Central

    Spear, T M; Svee, W; Vincent, J H; Stanisich, N

    1998-01-01

    The research presented in this article assessed geochemical factors relating to dust produced during primary lead smelting. Bulk dust samples and size-selective airborne dust samples were collected from four areas of a primary lead smelter and analyzed by X-ray diffraction and sequential chemical extraction. X-ray diffraction showed that the smelter dusts were composed primarily of sulfides, oxides, sulfates, and silicates of metal ores, with galena being the primary dust component. Sequential extraction revealed the solubility of lead compounds at less than 7% in the exchangeable and mildly acidic steps for the bulk dusts collected from four smelter areas. The later steps of the extraction procedure were more effective in dissolving the lead compounds associated with the bulk dust samples, with 43%, 26%, and 8% of the total lead, in the ore storage, sinter, and blast/dross smelter areas, respectively, being extracted in the residual step. Sequential extraction of coarse airborne dust samples from the ore storage and sinter plant showed that 1.2% and 4.1% of the total lead, respectively, was exchangeable. The finer particle size fractions from these areas of the smelter showed higher percentages of exchangeable lead. Of the course airborne dust from the blast/dross furnace processes, 65% of the total lead was exchangeable. However, the largest percentage of lead from these areas was associated with the finer particle-size fractions. If lead bioavailability is related to its solubility as determined through sequential extraction, the health hazards associated with lead exposure may be appreciably enhanced in the blast and dross furnace processes. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 PMID:9721256

  15. Raman spectroscopic studies of chemical speciation in calcium chloride melts

    SciTech Connect

    Windisch, Charles F.; Lavender, Curt A.

    2005-02-01

    Raman spectroscopy was applied to CaCl2 melts at 900 degrees C under both non-electrolyzed and electrolyzed conditions. The later used titania cathodes supplied by TIMET, Inc. and graphite anodes. Use of pulse-gating to collect the Raman spectra successfully eliminated any interference from black-body radiation and other stray light. The spectrum of molten CaCl2 exhibited no distinct, resolvable bands that could be correlated with a calcium chloride complex similar to MgCl42- in MgCl2 melts. Rather, the low frequency region of the spectrum was dominated by a broad “tail” arising from collective oscillations of both charge and mass in the molten salt “network.” Additions of both CaO and Ca at concentrations of a percent or two resulted in no new features in the spectra. Addition of CO2, both chemically and via electrolysis at concentrations dictated by stability and solubility at 900 degrees C and 1 bar pressure, also produced no new bands that could be correlated with either dissolved CO2 or the carbonate ion. These results indicated that Raman spectroscopy, at least under the conditions evaluated in the research, was not well suited for following the reactions and coordination chemistry of calcium ions, nor species such as dissolved metallic Ca and CO2 that are suspected to impact current efficiency in titanium electrolysis cells using molten CaCl2. Raman spectra of TIMET titania electrodes were successfully obtained as a function of temperature up to 900 degrees C, both in air and in-situ in CaCl2 melts. However, spectra of these electrodes could only be obtained when the material was in the unreduced state. When reduced, either with hydrogen or within an electrolysis cell, the resulting electrodes exhibited no measurable Raman bands under the conditions used in this work.

  16. Characterization of Chemical Speciation in Ultra Thin Uranium Oxide Films by Neutron Reflectometry

    SciTech Connect

    Wang, Peng

    2012-06-20

    Motivation for this project is due to more than 17 kg of HEU and 400 g of Pu have been interdicted through an international effort to control nuclear smuggling. Nuclear forensics - Detection and analysis of nuclear materials recovered from either the capture of unused materials or from the radioactive debris following a nuclear explosion or activities, which can contribute significantly for national security. Develop new nuclear forensic methods can be applied to: (a) Environmental swipes, (b) Small particulates, and (c) Thin films. Conclusions of the project are: (1) A unique approach: Neutron Reflectometry + Surface Enhanced Raman Spectroscopy; and (2) Detection of chemical speciation with {angstrom}-level resolution.

  17. Chemical speciation of trace metals emitted from Indonesian peat fires for health risk assessment

    NASA Astrophysics Data System (ADS)

    Betha, Raghu; Pradani, Maharani; Lestari, Puji; Joshi, Umid Man; Reid, Jeffrey S.; Balasubramanian, Rajasekhar

    2013-03-01

    Regional smoke-induced haze in Southeast Asia, caused by uncontrolled forest and peat fires in Indonesia, is of major environmental and health concern. In this study, we estimated carcinogenic and non-carcinogenic health risk due to exposure to fine particles (PM2.5) as emitted from peat fires at Kalimantan, Indonesia. For the health risk analysis, chemical speciation (exchangeable, reducible, oxidizable, and residual fractions) of 12 trace metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in PM2.5 was studied. Results indicate that Al, Fe and Ti together accounted for a major fraction of total metal concentrations (~ 83%) in PM2.5 emissions in the immediate vicinity of peat fires. Chemical speciation reveals that a major proportion of most of the metals, with the exception of Cr, Mn, Fe, Ni and Cd, was present in the residual fraction. The exchangeable fraction of metals, which represents their bioavailability, could play a major role in inducing human health effects of PM2.5. This fraction contained carcinogenic metals such as Cd (39.2 ng m- 3) and Ni (249.3 ng m- 3) that exceeded their WHO guideline values by several factors. Health risk estimates suggest that exposure to PM2.5 emissions in the vicinity of peat fires poses serious health threats.

  18. Heavy metals and its chemical speciation in sewage sludge at different stages of processing.

    PubMed

    Tytła, Malwina; Widziewicz, Kamila; Zielewicz, Ewa

    2016-01-01

    The analysis of heavy metal concentrations and forms in sewage sludge constitutes an important issue in terms of both health and environmental hazards the metals pose. The total heavy metals concentration enables only the assessment of its contamination. Hence the knowledge of chemical forms is required to determine their environmental mobility and sludge final disposal. Heavy metals speciation was studied by using four-stage sequential extraction BCR (Community Bureau of Reference). This study was aimed at determining the total concentration of selected heavy metals (Zn, Cu, Ni, Pb, Cd, Cr and Hg) and their chemical forms (except for Hg) in sludge collected at different stages of its processing at two municipal Wastewater Treatment Plants in southern Poland. Metals contents in sludge samples were determined by using flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). This study shows that Zn and Cu appeared to be the most abundant in sludge, while Cd and Hg were in the lowest concentrations. The sewage sludge revealed the domination of immobile fractions over the mobile ones. The oxidizable and residual forms were dominant for all the heavy metals. There was also a significant difference in metals speciation between sludges of different origin which was probably due to differences in wastewater composition and processes occurring in biological stage of wastewater treatment. The results indicate a negligible capability of metals to migrate from sludge into the environment. Our research revealed a significant impact of thickening, stabilization and hygienization on the distribution of heavy metals in sludge and their mobility.

  19. Linking the chemical speciation of cerium to its bioavailability in water for a freshwater alga.

    PubMed

    El-Akl, Philippe; Smith, Scott; Wilkinson, Kevin J

    2015-08-01

    Over the past decade, researchers have begun to use metals of the lanthanide family for numerous applications, including liquid crystal display (LCD) screens, optical fibers, and laser technology. Unfortunately, little is presently known about their bioavailability or the mechanisms by which they might cause toxicity. The present study focuses on cerium (Ce), one of the most widely used lanthanides, and on validating the biotic ligand model as a means to predict Ce bioaccumulation. Short-term exposures to Ce were performed using the unicellular alga Chlamydomonas reinhardtii, to better relate Ce bioavailability to its chemical speciation in solution. Maximum uptake fluxes (Jmax ) and affinity constants for the binding of Ce to the biological uptake sites (KS ) were established at pH 5.0 and pH 7.0. An apparent affinity constant of 1.8 × 10(7) M(-1) was observed at pH 5.0, with a larger value obtained at pH 7.0 (6 × 10(7) M(-1) ), albeit under conditions where equilibrium could not be confirmed. By evaluating Ce speciation using centrifugal ultrafiltration and single-particle inductively coupled plasma spectrometry, it could be concluded that very little (∼30%) Ce was truly dissolved at pH 7.0, with the majority of the metal being present in colloidal species. Speciation was also monitored by fluorescence to evaluate Ce complexation by natural organic matter (NOM). The presence of NOM decreased Ce bioaccumulation in line with free Ce concentrations. Finally, competition with calcium for the metal uptake sites was shown to result in a decrease in Ce uptake by C. reinhardtii. PMID:25772589

  20. U.S. National PM2.5 Chemical Speciation Monitoring Networks – CSN and IMPROVE: Description of Networks

    EPA Science Inventory

    The U.S. Environmental Protection Agency (EPA) initiated the national PM2.5 Chemical Speciation Monitoring Network (CSN) in 2000 to support evaluation of long-term trends and to better quantify the impact of sources on particulate matter (PM) concentrations in the size range belo...

  1. Chemical Speciation of PM-2.5 Collected During Prescribed Burns of the Coconino National Forest

    NASA Astrophysics Data System (ADS)

    Robinson, M.; Chavez, J.; Valazquez, S.

    2001-12-01

    In 1997, the EPA promulgated regulations for fine particulate matter (PM-2.5) due to concerns that PM-2.5 can contribute to pulmonary disease. A major source of PM-2.5 is smoke from forest fires (natural or prescribed). The use of prescribed fire is expected to increase in the next decade as a method for restoring wildland ecosystems. The fire-suppression policy of the past century has left forests overgrown with heavy fuel loads, increasing the likelihood of catastrophic fire. Prescribed fire, combined with mechanical thinning, is a method-of-choice to reduce this fuel load. The apparent conflict between the intentional use of fire and air quality can be addressed by increasing our understanding of PM-2.5 and its toxicity. To this end, we will monitor the chemical composition of PM-2.5 generated during three prescribed fires of the Coconino National Forest in October 2001. PM-2.5 will be collected using a battery-operated chemical speciation sampler (MetOne SuperSASS) positioned to collect smoke during the fire. Samples will be taken during the ignition and combustion phases, as well as the day after the burn. Each sampling period will collect 3 filters (PTFE, nylon + MgO denuder, and quartz), which will be analyzed (Research Triangle International) respectively for mass and elements, ions, and total, organic, and elemental carbon. In addition, a fourth PTFE filter will be collected and analyzed at NAU for lead isotope ratios using inductively-coupled plasma mass spectrometry. Results will be correlated to meteorological factors collected during the burns (relative humidity, wind speed, air stability, and surface temperature, etc.) and to characteristics of the burn itself (fuel load, fuel type, fire type, combustion phase, etc.). Results will be compared to the national database collected in EPA's PM-2.5 speciation trends monitoring network (STN).

  2. Impact of Environmentally Based Chemical Hardness on Uranium Speciation and Toxicity in Six Aquatic Species

    PubMed Central

    Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

    2015-01-01

    Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO42–) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. PMID:25475484

  3. Direct Measurement and Chemical Speciation of Top Ring Zone Liquid During Engine Operation

    SciTech Connect

    Splitter, Derek A; Burrows, Barry Clay; Lewis Sr, Samuel Arthur

    2015-01-01

    The present manuscript consists of proof of concept experiments involving direct measurements and detailed chemical speciation from the top ring zone of a running engine. The work uses a naturally aspirated single cylinder utility engine that has been modified to allow direct liquid sample acquisition from behind the top ring. Samples were analyzed and spectated using gas chromatographic techniques. Results show that the liquid mixture in the top ring zone is neither neat lubricant nor fuel but a combination of the two with unique chemical properties. At the tested steady state no-load operating condition, the chemical species of the top ring zone liquid were found to be highly dependent on boiling point, where both low reactivity higher boiling point fuel species and lubricant are observed to be the dominant constituents. The results show that at least for the tested condition, approximately 25% of the top ring zone is comprised of gasoline fuel like molecules, which are dominated by high octane number aromatic species, while the remainder of the liquid is comprised of lubricant like species.

  4. Modelling the chemical speciation of trace metals in the surface waters of the Humber system

    PubMed

    Tipping; Lofts; Lawlor

    1998-03-24

    Calculations have been performed to estimate the chemical speciation at equilibrium of six divalent trace metals (Co, Ni, Cu, Zn, Cd, Pb) in riverine, estuarine and marine surface waters of the Humber system. The Windermere Humic Aqueous Model (WHAM) was used to compute distributions of dissolved metals. In the rivers, the free aquo ion (M2+) is a major part of dissolved Co, Ni, Zn and Cd, but accounts for less than 1% of Cu and Pb. The main complexes are formed with carbonate ligands and dissolved natural organic matter, represented by fulvic acid. In the low-salinity region of the estuary and in seawater, complexation with fulvic acid is less significant, although most of the Cu is still in this form, while the speciation of Cd is dominated by chloride complexes. Adsorption of metals by suspended particulate matter was calculated with a simple model involving the concentrations of the free aquo ions (M2+) and H+, together with a constant for each metal estimated from laboratory adsorption data. Calculated adsorbed concentrations were used to predict the partition coefficient (KD) for each metal under different circumstances. The values can vary by an order of magnitude or more, depending upon solution conditions. Typical values for rivers, low-salinity water and seawater are within one order of magnitude of observations. However, there is a general tendency to underestimate KD, possible reasons being (1) neglect of electrostatic enhancement of adsorption at low ionic strengths; and (2) analytical overestimation of particulate metal in equilibrium with the solution phase. There is a strong case for the development of a more sophisticated adsorption model.

  5. Differences in Chemical Sexual Signals May Promote Reproductive Isolation and Cryptic Speciation between Iberian Wall Lizard Populations

    PubMed Central

    Gabirot, Marianne; López, Pilar; Martín, José

    2012-01-01

    Interpopulational variation in sexual signals may lead to premating reproductive isolation and speciation. Genetic and morphological studies suggest that the Iberian wall lizard, Podarcis hispanica, forms part of a “species complex” with several cryptic species. We explored the role of chemical sexual signals in interpopulational recognition between five distinct populations of Iberian wall lizards in Central Spain. Results showed that these populations differed in morphology and in composition and proportion of chemical compounds in femoral gland secretions of males. Tongue-flick experiments indicated that male and female lizards discriminated and were more interested in scents of lizards from their own area (i.e., Northern versus Southern populations), but did not discriminate between all populations. Moreover, only males from the populations that are geographically located more far away preferred scent of females from their own population. These data suggest that, at least between some populations, there may be reproductive isolation mediated by chemical signals and cryptic speciation. PMID:22288019

  6. Chemical speciation of chlorine in atmospheric aerosol samples by high-resolution proton induced X-ray emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Kertész, Zsófia; Furu, Enikő; Kavčič, Matjaž

    2013-01-01

    Chlorine is a main elemental component of atmospheric particulate matter (APM). The knowledge of the chemical form of chlorine is of primary importance for source apportionment and for estimation of health effects of APM. In this work the applicability of high-resolution wavelength dispersive proton induced X-ray emission (PIXE) spectroscopy for chemical speciation of chlorine in fine fraction atmospheric aerosols is studied. A Johansson-type crystal spectrometer with energy resolution below the natural linewidth of Cl K lines was used to record the high-resolution Kα and Kβ proton induced spectra of several reference Cl compounds and two atmospheric aerosol samples, which were collected for conventional PIXE analysis. The Kα spectra which refers to the oxidation state, showed very minor differences due to the high electronegativity of Cl. However, the Kβ spectra exhibited pronounced chemical effects which were significant enough to perform chemical speciation. The major chlorine component in two fine fraction aerosol samples collected during a 2010 winter campaign in Budapest was clearly identified as NaCl by comparing the high-resolution Cl Kβ spectra from the aerosol samples with the corresponding reference spectra. This work demonstrates the feasibility of high-resolution PIXE method for chemical speciation of Cl in aerosols.

  7. Impact of environmentally based chemical hardness on uranium speciation and toxicity in six aquatic species.

    PubMed

    Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

    2015-03-01

    Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO4 (2-) ) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. Environ Toxicol Chem 2015;34:562-574. © 2014 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC.

  8. Impact of environmentally based chemical hardness on uranium speciation and toxicity in six aquatic species.

    PubMed

    Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

    2015-03-01

    Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO4 (2-) ) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. Environ Toxicol Chem 2015;34:562-574. © 2014 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC. PMID:25475484

  9. Chemical Speciation and Quantitative Evaluation of Heavy Metal Pollution Hazards in Two Army Shooting Range Backstop Soils.

    PubMed

    Islam, Mohammad Nazrul; Nguyen, Xuan Phuc; Jung, Ho-Young; Park, Jeong-Hun

    2016-02-01

    The chemical speciation and ecological risk assessment of heavy metals in two shooting range backstop soils in Korea were studied. Both soils were highly contaminated with Cd, Cu, Pb, and Sb. The chemical speciation of heavy metals reflected the present status of contamination, which could help in promoting management practices. We-rye soil had a higher proportion of exchangeable and carbonate bound metals and water-extractable Cd and Sb than the Cho-do soil. Bioavailable Pb represented 42 % of the total Pb content in both soils. A significant amount of Sb was found in the two most bioavailable fractions, amounting to ~32 % in the soil samples, in good agreement with the batch leaching test using water. Based on the values of ecological risk indices, both soils showed extremely high potential risk and may represent serious environmental problems.

  10. Chemical-thermal quantitative methodology for carbon speciation in damage layers on building surfaces.

    PubMed

    Ghedini, Nadia; Sabbioni, Cristina; Bonazza, Alessandra; Gobbi, Giancarlo

    2006-02-01

    The issue of environment protection, including the conservation of the monumental heritage worldwide, is related to atmospheric pollution, and its future therefore depends on air pollutant reduction. Carbonaceous particles emitted by combustion processes are the main factors responsible for the blackening of buildings. The identification and evaluation of the carbon species constituting the noncarbonate fraction of total carbon in damage layers, particularly in urban areas, are required in orderto investigate atmospheric deposition on building surfaces. Since noncarbonate carbon contains organic and elemental carbon originating from various human activities, its measurement and speciation are crucial to the protection and conservation of monuments and ancient masonry, playing an important role both in the proposal of mitigation strategies and in the definition of conservation treatments. The availability of a correct, accurate, and reproducible analytical method for a complete carbon balance is essential in studying the effects of atmospheric pollutants on the environment, including those affecting cultural heritage. A chemical-thermal methodology was set up, and its sensitivity, accuracy, repeatability, and reproducibility were tested on appropriate standard samples of composition similar to the black crusts on stones and mortars. The results indicate thatthe technique satisfactorily distinguishes among carbon species, particularly those of anthropogenic origin, allowing a reliable evaluation of their quantities in damage layers. In view of the difficulties encountered in applying the thermo-optical methods adopted for the measurement of carbon filters, the proposed methodology contributes to filling the current gap in suitable and reliable analytical procedures in the field of cultural heritage protection. PMID:16509340

  11. The toxicology of chromium with respect to its chemical speciation: a review.

    PubMed

    Katz, S A; Salem, H

    1993-01-01

    The properties of trivalent and hexavalent chromium are reviewed with respect to acute and chronic oral toxicity, dermal toxicity, systemic toxicity, toxicokinetics, cytotoxicity, genotoxicity and carcinogenicity. The hexavalent chromium compounds appear to be 10-100 times more toxic than the trivalent chromium compounds when both are administered by the oral route. Dermal irritancy and allergy are more frequently caused by contact with soluble hexavalent chromium compounds. The cytotoxicity of soluble and insoluble hexavalent chromium compounds to fibroblasts is 100-1000 times greater than that demonstrated by trivalent chromium compounds. In short-term tests, the hexavalent chromium compounds demonstrated genotoxic effects four times more frequently than did the trivalent chromium compounds. Carcinogenicity appears to be associated with the inhalation of the less soluble/insoluble hexavalent chromium compounds. The toxicology of chromium does not reside with the elemental form. It varies greatly among a wide variety of very different chromium compounds. Oxidation state and solubility are particularly important factors in considering the toxicity of chromium with respect to its chemical speciation.

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

    SciTech Connect

    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 mechanism onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction desorption tests and U L{sub 3}-edge X-ray absorption near-edge structure (XANES) spectroscopy of contaminated wetland sediments. 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 tests indicated that the U(VI) species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and NOM fraction (Na-pyrophosphate extractable). Uranium L3- edge XANES spectra of the U-retained sediments were nearly identical to that of uranyl acetate. The primary oxidation state of U in these sediments was as 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. The molecular mechanism responsible for the high U retention in the SRS wetland sediments is likely related to the chemical bonding of U to organic carbon.

  13. Plant absorption of trace elements in sludge amended soils and correlation with soil chemical speciation.

    PubMed

    Torri, Silvana; Lavado, Raúl

    2009-07-30

    The aim of the present study was to investigate the relationship between Lolium perenne L. uptake of Cd, Cu, Pb, and Zn in sludge amended soils and soil availability of these elements assessed by soil sequential extraction. A greenhouse experiment was set with three representative soils of the Pampas Region, Argentina, amended with sewage sludge and sewage sludge enriched with its own incinerated ash. After the stabilization period of 60 days, half of the pots were sampled for soil analysis; the rest of the pots were sown with L. perenne and harvested 8, 12, 16 and 20 weeks after sowing, by cutting just above the soil surface. Cadmium and Pb concentrations in aerial tissues of L. perenne were below detection limits, in good agreement with the soil fractionation study. Copper and Zn concentration in the first harvest were significantly higher in the coarse textured soil compared to the fine textured soil, in contrast with soil chemical speciation. In the third harvest, there was a positive correlation between Cu and Zn concentration in aerial biomass and soil fractions usually considered of low availability. We conclude that the most available fractions obtained by soil sequential extraction did not provide the best indicator of Cu and Zn availability to L. perenne.

  14. Speciation and chemical activities in superheated sodium borate solutions. Final report

    SciTech Connect

    Weres, O.

    1993-06-01

    The system H{sub 2}O-B{sub 2}O{sub 3}-Na{sub 2}O has been studied experimentally at 277{degrees} and 317{degrees}C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modelled using the Pitzer-Simonson Model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. These data will allow prediction of the composition and chemical behavior of sodium borate liquids that may accumulate in the superheated crevices within a steam generator. A modified form of the model is provided for use with MULTEQ. The potassium borate system also was briefly studied at 317{degrees}C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B = 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.

  15. Chemical-thermal quantitative methodology for carbon speciation in damage layers on building surfaces.

    PubMed

    Ghedini, Nadia; Sabbioni, Cristina; Bonazza, Alessandra; Gobbi, Giancarlo

    2006-02-01

    The issue of environment protection, including the conservation of the monumental heritage worldwide, is related to atmospheric pollution, and its future therefore depends on air pollutant reduction. Carbonaceous particles emitted by combustion processes are the main factors responsible for the blackening of buildings. The identification and evaluation of the carbon species constituting the noncarbonate fraction of total carbon in damage layers, particularly in urban areas, are required in orderto investigate atmospheric deposition on building surfaces. Since noncarbonate carbon contains organic and elemental carbon originating from various human activities, its measurement and speciation are crucial to the protection and conservation of monuments and ancient masonry, playing an important role both in the proposal of mitigation strategies and in the definition of conservation treatments. The availability of a correct, accurate, and reproducible analytical method for a complete carbon balance is essential in studying the effects of atmospheric pollutants on the environment, including those affecting cultural heritage. A chemical-thermal methodology was set up, and its sensitivity, accuracy, repeatability, and reproducibility were tested on appropriate standard samples of composition similar to the black crusts on stones and mortars. The results indicate thatthe technique satisfactorily distinguishes among carbon species, particularly those of anthropogenic origin, allowing a reliable evaluation of their quantities in damage layers. In view of the difficulties encountered in applying the thermo-optical methods adopted for the measurement of carbon filters, the proposed methodology contributes to filling the current gap in suitable and reliable analytical procedures in the field of cultural heritage protection.

  16. Chemical Speciation and Potential Mobility of Heavy Metals in the Soil of Former Tin Mining Catchment

    PubMed Central

    Ashraf, M. A.; Maah, M. J.; Yusoff, I.

    2012-01-01

    This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As. PMID:22566758

  17. Chemical speciation of iron in seawater by cathodic stripping voltammetry with dihydroxynaphthalene.

    PubMed

    van den Berg, Constant M G

    2006-01-01

    The chemical speciation of iron in seawater is determined by cathodic stripping voltammetry using 2,3-dihydroxynaphthalene (DHN) as adsorptive and competing ligand. The optimized conditions include a DHN concentration of 0.5-1 microM, seawater at its original pH of 8, and equilibration overnight. The alpha-coefficient for DHN (=[FeDHN]/[Fe']) was calibrated against EDTA giving values of 166 for 0.5 microM DHN and 366 at 1 microM DHN and a value of 8.51 +/- 0.07 for log K'(Fe'DHN). The dissociation of the natural iron species FeL was found to have a characteristic reaction time of 50 min, indicating that titrations should be equilibrated overnight rather than the shorter periods sometimes used onboard ship. The method was applied to samples from the Pacific giving ligand concentrations of 1.1 and 1.6 nM for deep and surface waters, respectively, with an average value for log K'(FeL) of 11.9 +/- 0.3 compared to a value of 11.5 for the siderophore deferoxamine. The results are similar to those obtained previously for similar samples, but the new method has much greater sensitivity for iron than previous methods, leading to lower limits of detection and shorter analysis time.

  18. Organic Nitrogen in Atmospheric Drops and Particles: Concentrations, (Limited) Speciation, and Chemical Transformations

    NASA Astrophysics Data System (ADS)

    Anastasio, C.; Zhang, Q.

    2003-12-01

    While quite a bit is known of the concentrations, speciation, and chemistry of inorganic forms of nitrogen in the atmosphere, the same cannot be said for organic forms. Despite this, there is growing evidence that organic N (ON) is ubiquitous in the atmosphere, especially in atmospheric condensed phases such as fog/cloud drops and aerosol particles. Although the major compounds that make up organic N are generally unknown, as are the sources of these compounds, it is clear that there are significant fluxes of ON between the atmosphere and ecosystems. It also appears that organic N can have significant effects in both spheres. The goal of our recent work in this area has been to better describe the atmospheric component of the biogeochemistry of organic nitrogen. Based on particle, gas, and fogwater samples from Northern California we have made three major findings: 1) Organic N represents a significant component, approximately 20%, of the total atmospheric N loading in these samples. This is broadly consistent with studies from other locations. 2) Amino compounds, primarily as combined amino acids, account for approximately 20% of the measured ON in our condensed phase samples. Given the properties of amino acids, these compounds could significantly affect the chemical and physical properties of atmospheric particles. 3) Organic nitrogen in atmospheric particles and drops is transformed to inorganic forms - primarily ammonium, nitrate, and nitrogen oxides (NOx) - during exposure to sunlight and/or ozone. These chemical reactions likely increase the bioavailability of the condensed phase nitrogen pool and enhance its biological effects after deposition to ecosystems.

  19. 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...

  20. Chemical Speciation of Strontium, Americium, and Curium in High Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    CHOPPIN, GREGORY R.

    2003-06-01

    The objective of this research project is to measure the effects of organic chelate complexation on the speciation and solubility of Sr and trivalent actinides under strongly basic, high carbonate conditions, similar to those present in high- level waste tanks at U.S. Department of Energy storage sites. We proposed, (1) extension to important chelates not previously studied; (2) studies of completing metal ions; and (3) specific studies using Am(III)/Cm(III). The chelate complexation studies would extend our previous research on EDTA, HEDTA, NTA, and IDA to citrate and oxalate. In addition, we propose to address the possible formation of mixed ligand- ligand complexes for Eu(III) in EDTA-HEDTA, EDTA-NTA, HEDTA-NTA, and ligand-carbonate solutions. The fundamental data on chemical speciation and solubility will be used to develop accurate thermodynamic models which are valid to high ionic strength.

  1. Mercury speciation modeling using site specific chemical and redox data from the TNXOD OU

    SciTech Connect

    Kaplan, D.I.

    2000-03-22

    The objective of this study was to evaluate mercury speciation under reducing conditions expected in sediments at the TNX Outfall Delta Operable Unit. These changes in speciation would then be used to infer whether mercury toxicity and mobility would be expected to be significantly altered under reducing conditions. The results from this work suggest that mercury would likely become more strongly retained by the solid phase under reducing conditions than under oxidizing conditions at the TNX Outfall Delta Site. Considering that experimental results indicate that mercury is extremely tightly bound to the solid phase under oxidizing conditions, little mercury mobility would therefore be expected under reducing conditions.

  2. Cadmium chemical speciation and absorption in plant in a polluted soil

    NASA Astrophysics Data System (ADS)

    Gigliotti, Giovanni; Massaccesi, Luisa

    2013-04-01

    speciation results showed that a significant amount of Cd (45%), before plant seeding, was associated with the metal oxide fraction (typically Fe-Mn oxides and hydroxides) followed to Cd bound to soil organic matter (39%), despite the content of organic matter in the soil was very low. Instead the amount of Cd bound to carbonates (13%), exchangeable phase (1%) and residue fraction (2.5%) were negligible. After six weeks of plant seeding the Cd fractionation was slightly different, with a decrease of metal bound to oxide and hydroxide from 45% to 29% and an increase of fraction bound to carbonate from 13% to 19% and exchangeable fraction from 1% to 8%. The roots system of Festuca had colonized all pot and the fractionation of metal was disturbed by plants growth. Roots may induce changes in the biochemical, chemical and physical properties of the rhizosphere increasing potentially toxic elements diffusion through the production of roots exudates. The soil environment immediately adjacent to the root can be strongly influenced by root exudates, so that chemical process of dissolution, chelation and precipitation outside the root also occur. Cd was absorbed by plant root in a great concentration, but not translocation to leafs was noticed.

  3. The role of chemical speciation, chemical fractionation and calcium disruption in manganese-induced developmental toxicity in zebrafish (Danio rerio) embryos.

    PubMed

    Hernández, R B; Nishita, M I; Espósito, B P; Scholz, S; Michalke, B

    2015-10-01

    Manganese (Mn) is an essential nutrient that can be toxic in excess concentrations, especially during early development stages. The mechanisms of Mn toxicity is still unclear, and little information is available regarding the role of Mn speciation and fractionation in toxicology. We aimed to investigate the toxic effects of several chemical forms of Mn in embryos of Danio rerio exposed during different development stages, between 2 and 122h post fertilization. We found a stage-specific increase of lethality associated with hatching and removal of the chorion. Mn(II), ([Mn(H2O)6](2+)) appeared to be the most toxic species to embryos exposed for 48h, and Mn(II) citrate was most toxic to embryos exposed for 72 and/or 120h. Manganese toxicity was associated with calcium disruption, manganese speciation and metal fractionation, including bioaccumulation in tissue, granule fractions, organelles and denaturated proteins.

  4. Chemical speciation in waters influenced by lead-zinc metallurgical industry.

    PubMed

    Tepavitcharova, Stefka; Todorov, Tihomir; Dassenakis, Manos; Paraskevopoulou, Vasiliki

    2010-10-01

    The Lead-Zinc Company region, Kardjali city, Bulgaria, is known to be highly polluted with heavy metals from its pyrometallurgical activities. The polluted levels and the chemical speciation in surface natural waters in the region as well as in the wastewaters of the factory were investigated in January 2008 by application of monitoring studies, thermodynamic modeling, and interpretation in terms of the "softness-hardness" factor. It was found that the levels of trace metals pollution of surface waters were lower than the legislation limits for the regions with Pb and Zn production. The wastewater treatment facilities of the company were found to operate properly, and the quality of the cleaned waters in station Kar4 was comparable to the other surface waters studied (e.g., station Kar5). The trace metals were divided into three groups: (1) Fe(3+) and Al(3+), being "hard" acids, existed in all the studied waters as hydroxy species Fe(OH)2(+), AlOH(2+), and Al(OH)2(+), followed by the phosphate species AlPO4(0) and Al(2)(OH)(2)PO4(0); (2) Mn(2+), Zn(2+), and Cd(2+) being "soft" acids with crystal field stabilization energy (CFSE) = 0 were present in natural waters mainly as free Me(2+) ions. Small concentrations of their MeSO4(0), MeCO3(0) species, and of MeCl2(0) (Me = Zn, Cd) species were also calculated. In the wastewaters, two more species [Me(SO4)2(2-) and Me(SO4)3(4-)] of the softer Zn and Cd metals were also calculated; (3) Cu(2+) and Pb(2+), as "soft" acids with CFSE not equal to 0 preferentially coordinated with softer CO3(2-) ions and in natural waters existed mainly as MeCO3(0) and PbHCO3(+), followed by free Me(2+)ions and MeOH(+). In the wastewaters, MeSO4(0) and Pb(SO4)2(2-) species increased at the expense of the free Me(2+) ions. The highest self-cleaning capability of natural waters was found with respect to Al and Fe, followed by Mn and Cd. The lowest corresponded to Pb, Cu, and Zn.

  5. Effects of Particle Size on Chemical Speciation and Bioavailability of Copper to Earthworms ( Eisenia fetida ) Exposed to Copper Nanoparticles

    SciTech Connect

    J Unrine; O Tsyusko; S Hunyadi; J Judy; P Bertsch

    2011-12-31

    To investigate the role of particle size on the oxidation, bioavailability, and adverse effects of manufactured Cu nanoparticles (NPs) in soils, we exposed the earthworm Eisenia fetida to a series of concentrations of commercially produced NPs labeled as 20- to 40-nm or <100-nm Cu in artificial soil media. Effects on growth, mortality, reproduction, and expression of a variety of genes associated with metal homeostasis, general stress, and oxidative stress were measured. We also used X-ray absorption spectroscopy and scanning X-ray fluorescence microscopy to characterize changes in chemical speciation and spatial distribution of the NPs in soil media and earthworm tissues. Exposure concentrations of Cu NPs up to 65 mg kg{sup -1} caused no adverse effects on ecologically relevant endpoints. Increases in metallothionein expression occurred at concentrations exceeding 20 mg kg-1 of Cu NPs and concentrations exceeding 10 mg kg{sup -1} of CuSO{sub 4} Based on the relationship of Cu tissue concentration to metallothionein expression level and the spatial distribution and chemical speciation of Cu in the tissues, we conclude that Cu ions and oxidized Cu NPs were taken up by the earthworms. This study suggests that oxidized Cu NPs may enter food chains from soil but that adverse effects in earthworms are likely to occur only at relatively high concentrations (>65 mg Cu kg{sup -1} soil).

  6. Chemical speciation and enzymatic impact of silver in antimicrobial fabric buried in soil.

    PubMed

    Takeuchi, Satoshi; Hashimoto, Yohey; Yamaguchi, Noriko; Toyota, Koki

    2016-11-01

    This study investigated the impact of Ag in antibacterial fabric on soil enzymes in relation to solubility and speciation of Ag. Sections of Ag-containing sock fabric (1.0-1.5cm(2)) were incubated in soils with aerobic and anaerobic conditions and periodically determined activity of arylsulfatase, dehydrogenase and urease. Microscale distribution and speciation of Ag at the interface between socks and soil particles were investigated using micro-focused X-ray fluorescence (μ-XRF), and Ag speciation was determined using micro-focused X-ray absorption near edge structure (μ-XANES) spectroscopy. Results showed that the sock fabric consisted of elemental Ag and Ag2S. After 60-day exposure to soil, majority (50-90%) of Ag in sock did not undergo phase transformation and present as elemental Ag and Ag2S in aerobic and anaerobic conditions. A part of Ag in sock fabric was bound with soil colloids (<15%), depending on the distance from the edge of sock fabric. Soil enzyme activities were overall unaffected by Ag in sock textile after 60days of incubation, although a significant decrease in arylsulfatase activity was found only in the initial stage of soil incubation. Silver in the sock fabric is relatively stable and has little detrimental impacts on enzyme activity in ordinary soil conditions. PMID:27351904

  7. Chemical speciation and enzymatic impact of silver in antimicrobial fabric buried in soil.

    PubMed

    Takeuchi, Satoshi; Hashimoto, Yohey; Yamaguchi, Noriko; Toyota, Koki

    2016-11-01

    This study investigated the impact of Ag in antibacterial fabric on soil enzymes in relation to solubility and speciation of Ag. Sections of Ag-containing sock fabric (1.0-1.5cm(2)) were incubated in soils with aerobic and anaerobic conditions and periodically determined activity of arylsulfatase, dehydrogenase and urease. Microscale distribution and speciation of Ag at the interface between socks and soil particles were investigated using micro-focused X-ray fluorescence (μ-XRF), and Ag speciation was determined using micro-focused X-ray absorption near edge structure (μ-XANES) spectroscopy. Results showed that the sock fabric consisted of elemental Ag and Ag2S. After 60-day exposure to soil, majority (50-90%) of Ag in sock did not undergo phase transformation and present as elemental Ag and Ag2S in aerobic and anaerobic conditions. A part of Ag in sock fabric was bound with soil colloids (<15%), depending on the distance from the edge of sock fabric. Soil enzyme activities were overall unaffected by Ag in sock textile after 60days of incubation, although a significant decrease in arylsulfatase activity was found only in the initial stage of soil incubation. Silver in the sock fabric is relatively stable and has little detrimental impacts on enzyme activity in ordinary soil conditions.

  8. Chemical speciation of neptunium in spent fuel. Annual report for period 15 August 1999 to 15 August 2000

    SciTech Connect

    Ken Czerwinski; Don Reed

    2000-09-01

    (B204) This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste. Another important aspect of this project is the close cooperation between a university and a national laboratory. The PI has a transuranic laboratory at MIT where

  9. Chemical fractionation and speciation modelling for optimization of ion-exchange processes to recover palladium from industrial wastewater.

    PubMed

    Folens, K; Van Hulle, S; Vanhaecke, F; Du Laing, G

    2016-01-01

    Palladium is used in several industrial applications and, given its high intrinsic value, intense efforts are made to recover the element. In this hydrometallurgic perspective, ion-exchange (IEX) technologies are principal means. Yet, without incorporating the chemical and physical properties of the Pd present in real, plant-specific conditions, the recovery cannot reach its technical nor economic optimum. This study characterized a relevant Pd-containing waste stream of a mirror manufacturer to provide input for a speciation model, predicting the Pd speciation as a function of pH and chloride concentration. Besides the administered neutral PdCl2 form, both positively and negatively charged [PdCln](2-n) species occur depending on the chloride concentration in solution. Purolite C100 and Relite 2AS IEX resins were selected and applied in combination with other treatment steps to optimize the Pd recovery. A combination of the cation and anion exchange resins was found successful to quantitatively recover Pd. Given the fact that Pd was also primarily associated with particles, laboratory-scale experiments focused on physical removal of the Pd-containing flow were conducted, which showed that particle-bound Pd can already be removed by physical pre-treatment prior to IEX, while the ionic fraction remains fully susceptible to the IEX mechanism. PMID:27054747

  10. Chemical fractionation and speciation modelling for optimization of ion-exchange processes to recover palladium from industrial wastewater.

    PubMed

    Folens, K; Van Hulle, S; Vanhaecke, F; Du Laing, G

    2016-01-01

    Palladium is used in several industrial applications and, given its high intrinsic value, intense efforts are made to recover the element. In this hydrometallurgic perspective, ion-exchange (IEX) technologies are principal means. Yet, without incorporating the chemical and physical properties of the Pd present in real, plant-specific conditions, the recovery cannot reach its technical nor economic optimum. This study characterized a relevant Pd-containing waste stream of a mirror manufacturer to provide input for a speciation model, predicting the Pd speciation as a function of pH and chloride concentration. Besides the administered neutral PdCl2 form, both positively and negatively charged [PdCln](2-n) species occur depending on the chloride concentration in solution. Purolite C100 and Relite 2AS IEX resins were selected and applied in combination with other treatment steps to optimize the Pd recovery. A combination of the cation and anion exchange resins was found successful to quantitatively recover Pd. Given the fact that Pd was also primarily associated with particles, laboratory-scale experiments focused on physical removal of the Pd-containing flow were conducted, which showed that particle-bound Pd can already be removed by physical pre-treatment prior to IEX, while the ionic fraction remains fully susceptible to the IEX mechanism.

  11. Chemical Speciation and Oxidation Kinetics of Iron and Sulfur in Subseafloor Basement Fluids on the Juan de Fuca Ridge Flanks

    NASA Astrophysics Data System (ADS)

    Glazer, B. T.; Matzinger, M.; Cowen, J. P.

    2011-12-01

    Redox reactive chemical species circulate throughout the upper oceanic crust, and are involved in a variety of abiotic and microbially-mediated reactions. Through exchange with bottom seawater, fluids circulating in the upper basement have the potential to influence scales ranging from global-scale biogeochemical cycling to micro-scale microbe-mineral interactions. Understanding fundamental chemical speciation, distribution, bioavailability, and rates of transformations for key chemical redox species is crucial to understanding processes in the subsurface. In-situ electrochemical analyses were conducted in real-time at CORK (Circulation Obviation Retrofit Kit) observatories affixed to Integrated Ocean Drilling Program (IODP) boreholes in Cascadia Basin on the Juan de Fuca Ridge Flanks. Voltammetric electrodes were mounted into a flow cell to allow for simultaneous detection of redox species (O2, H_{2}O2, HS^{-}, S(0), Sx^{2-}, S2O_{3}2-, S_{4}O6^{2-}, Fe(II), Fe(III), FeS$_{(aq)}) concurrent to sample filtering or fluid collection. During real-time voltammetric scanning, qualitative assessment of the integrity of fluids delivered through the Fluid Delivery Lines could be made, allowing for comparisons between CORK sites and various sampling strategies. Newly installed CORKs at IODP sites 1362A and 1362B are producing the highest-integrity basement fluids collected to date, deplete in oxygen (<3uM) and enriched in iron (>1uM). Here, we report results of in situ electrochemical measurements at multiple borehole observatories, including the newly installed 1362A & 1362B sites, and present results of speciation analyses and kinetics of oxidation for iron and sulfur in discrete samples.

  12. Programmable thermal dissociation of reactive gaseous mercury - a potential approach to chemical speciation: results from a field study

    NASA Astrophysics Data System (ADS)

    Tatum Ernest, C.; Donohoue, D.; Bauer, D.; Ter Schure, A.; Hynes, A. J.

    2012-12-01

    The use of programmable thermal dissociation (PTD) as an approach to investigating the chemical speciation of reactive gaseous mercury (RGM, Hg2+) has been explored in a field study. In this approach RGM is collected on a denuder and analyzed using PTD. The denuder is placed in an oven and the dissociation of the RGM is measured, as a function of temperature, by monitoring the evolution of elemental mercury (GEM, Hg0) in real time using laser-induced fluorescence (LIF). The technique was tested in a field campaign at a coal-fired power plant in Pensacola, Florida. Uncoated tubular denuders were used to obtain samples from the plant's stack exhaust gases and from the stack plume, downwind of the stack using an airship. The PTD profiles from these samples were compared with PTD profiles of HgCl2.

  13. Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in downtown Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

    2014-07-01

    Currently, there are a limited number of field studies that evaluate the long-term performance of the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. Intercomparison of two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21) indicating that ACSM instruments are capable of stable and reproducible operation. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the filter-adjusted continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Correlations of the ACSM NR-PM1 (non-refractory particulate matter with aerodynamic diameter less than or equal to 1 μm) plus elemental carbon (EC) with tapered element oscillating microbalance (TEOM) PM2.5 and Federal Reference Method (FRM) PM1 mass are strong with r2 > 0.7 and r2 > 0.8, respectively. Discrepancies might be attributed to evaporative losses of semi-volatile species from the filter measurements used to adjust the collocated continuous measurements. This suggests that adjusting the ambient aerosol continuous measurements with results from filter analysis introduced additional bias to the measurements. We also recommend to calibrate the ambient aerosol monitoring instruments using aerosol standards rather than gas-phase standards. The fitting approach for ACSM relative ionization for sulfate was shown to improve the comparisons between ACSM and collocated measurements in the absence of calibrated values, suggesting the importance of adding sulfate calibration into the ACSM calibration routine.

  14. [Application of Tessier-AAS to the non-biological transformation mechanism of chemical speciation of lead in red soil in agricultural area of central China].

    PubMed

    Fan, Chun-hui; Zhang, Ying-chao; Wang, Jia-hong

    2015-02-01

    The soil contamination of heavy metals, from the areas of mine, highway, industrial area, agricultural land and so on, is nowadays a serious issue all over the world. The contamination of heavy metals in large agricultural area might lead to the decrease of products quality and economic value. Actually, the accumulation amount of heavy metals by crops is much more related to the activated speciation, which is exchangeable and able to transform to the forms of carbonates, Fe-Mn oxides, organic matter and residual. Thus, the investigation to reveal the transformation mechanism of heavy metals caused by soil conditions might be appropriate to reduce the contaminated risk to crops. The vermicular red soil from the agricultural area of central China was used as sample in the paper, and the Tessier Sequential Extraction Procedure-atomic absorption spectroscopy (AAS) was applied to discuss the chemical speciation and non-biological transformation mechanism of Pb at different conditions. The results showed: the total amount of Pb is 32.56 mg x kg(-1), lower than the first level of the State Environmental Quality Standard for Soils. The Pb content of different speciation, with decreased concentration, is residual (54.55% of total Pb content), bound to Fe-Mn oxides, bound to organic matter, bound to carbonates and exchangeable. The pH value of red soil is related to the charge amount on surface of inorganic colloids and organic matter, and the water content of red soil would change the redox potential, effective for the variation of chemical speciation of Pb. The environmental factors of straw dosage and aging time could change Pb speciation, with Pb concentration of residual form the highest. The Muller index of Igeo is 0.3025, indicating the contribution of human activities. The Tessier Sequential Extraction Procedure-AAS is effective for the non-biological transformation mechanism identification of Pb speciation in red soil.

  15. The Effects of Soil Type and Chemical Treatment on Nickel Speciation in Refinery Enriched Soils: A Multi-Technique Investigation

    SciTech Connect

    McNear, Jr.,D.; Chaney, R.; Sparks, D.

    2007-01-01

    Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km{sup 2} of land with Ni concentrations exceeding the Canadian Ministry of the Environment's remedial action level of 200 mg kg{sup -1}. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale 'Kotodesh', a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability. Stirred-flow dissolution experiments using pH 4 HNO{sub 3} showed that Ni release from the limed Quarry muck and Welland loam soils was reduced ({approx}0.10%) relative to the unlimed soils ({approx}2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 {mu}m in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils. The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne

  16. The effects of soil type and chemical treatment on nickel speciation in refinery enriched soils: A multi-technique investigation

    NASA Astrophysics Data System (ADS)

    McNear, David H.; Chaney, Rufus L.; Sparks, Donald L.

    2007-05-01

    Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km 2 of land with Ni concentrations exceeding the Canadian Ministry of the Environment's remedial action level of 200 mg kg -1. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale 'Kotodesh', a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability. Stirred-flow dissolution experiments using pH 4 HNO 3 showed that Ni release from the limed Quarry muck and Welland loam soils was reduced (˜0.10%) relative to the unlimed soils (˜2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 μm in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils. The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne refinery. We provide the first

  17. 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.

  18. [Phytoavailability and chemical speciation of cadmium in different Cd-contaminated soils with crop root return].

    PubMed

    Zhang, Jing; Yu, Ling-Ling; Xin, Shu-Zhen; Su, De-Chun

    2013-02-01

    Pot experiments were conducted under greenhouse condition to investigate the effects of crop root return on succeeding crops growth, Cd uptake and soil Cd speciation in Cd-contaminated soil and artificial Cd-contaminated soil. The results showed that the amount of root residue returned to soil by corn and kidney bean growth successive for 3 times was 0.4%-1.1%. The Cd returned to soil by root residue was 1.3%-3.5% to the total soil Cd. There was no significant difference in the shoot dry weights of winter wheat and Chinese cabbage grown on the 2 Cd-contaminated soils with and without root return. While Cd concentration of Chinese cabbage increased significantly in the Cd-contaminated soil with corn or kidney bean root return. Light fraction of soil organic matter increased with root return in both of the Cd-contaminated soils. The percentage of Cd in the light fraction of soil organic matter increased with root return in the artificial Cd-contaminated soil. Soil carbonates-bound Cd concentration decreased significantly with corn root return in the Cd-contaminated soil. Soil exchangeable Cd concentration decreased and soil Fe-Mn oxide-bound Cd concentration increased significantly with kidney bean root return in the artificial Cd-contaminated soil.

  19. Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water.

    PubMed

    Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F Javier; Alvarez-Puebla, Ramon A

    2014-07-21

    Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg(2+) and the more toxicologically relevant methylmercury (CH₃Hg(+)) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg(2+) and CH₃Hg(+) to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.

  20. Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water.

    PubMed

    Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F Javier; Alvarez-Puebla, Ramon A

    2014-07-21

    Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg(2+) and the more toxicologically relevant methylmercury (CH₃Hg(+)) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg(2+) and CH₃Hg(+) to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms. PMID:24938410

  1. Evaluation of the chemically speciated particulate matter from a high-resolution air quality modeling system over the Iberian Peninsula

    NASA Astrophysics Data System (ADS)

    Pay, M. T.; Piot, M.; Jimenez-Guerrero, P.; Jorba, O.; Perez, C.; Baldasano, J. M.

    2009-04-01

    Particulate matter (PM) is a complex mixture of many compounds, both natural and anthropogenic; that determines its compositions and size. In addition, it is influenced by multiple atmospheric physico-chemical processes that can affect this matter from its release point, as a primary aerosol, or via gas-to-particle conversion processes that give rise to secondary aerosols. Inter-comparisons of European air quality models at regional and urban scales show that models tend to underestimate the observed concentrations of PM10 and PM2.5. Definitely, an accurate representation of the chemically speciated aerosols compounds is required in order to adequately simulate PM concentrations. The Barcelona Supercomputing Center-Centro Nacional de Supercomputacion (BSC-CNS) currently operates high-resolution air quality forecasts for Europe (12km, 1hr) and the Iberian Peninsula (4km, 1hr) with WRF-ARW/HERMES/CMAQ/DREAM modelling system under the umbrella of the CALIOPE project (http://www.bsc.es/caliope/) and Saharan dust forecasts with BSC-DREAM (http://www.bsc.es/projects/earthscience/DREAM/). In this framework, PM10 and PM2.5 products in both domains are achieved adding the Saharan dust contribution from DREAM (8 bins version) to the anthropogenic output of CMAQ. Furthermore, the CMAQ version used for this modelling system includes the contribution of sea salt aerosols. Eleven different chemical aerosol components can be distinguished, namely nitrates, sulphates, ammonium, elemental carbon, organic carbon with three subcomponents: primary, secondary anthropogenic and secondary biogenic, soil, sodium, chlorine and mineral dust. This study is focused on the evaluation of these aforementioned aerosol compounds from WRF-ARW/HERMES/CMAQ/DREAM over the Iberian Peninsula domain for the year 2004. The model evaluation with respect to the individual aerosol components has been performed for the domains of study. Albeit PM composition evaluation is presently hampered by the lack of

  2. Chemical speciation of vanadium in particulate matter emitted from diesel vehicles and urban atmospheric aerosols.

    PubMed

    Shafer, Martin M; Toner, Brandy M; Overdier, Joel T; Schauer, James J; Fakra, Sirine C; Hu, Shaohua; Herner, Jorn D; Ayala, Alberto

    2012-01-01

    We report on the development and application of an integrated set of analytical tools that enable accurate measurement of total, extractable, and, importantly, the oxidation state of vanadium in sub-milligram masses of environmental aerosols and solids. Through rigorous control of blanks, application of magnetic-sector-ICPMS, and miniaturization of the extraction/separation methods we have substantially improved upon published quantification limits. The study focused on the application of these methods to particulate matter (PM) emissions from diesel vehicles, both in baseline configuration without after-treatment and also equipped with advanced PM and NO(x) emission controls. Particle size-resolved vanadium speciation data were obtained from dynamometer samples containing total vanadium pools of only 0.2-2 ng and provide some of the first measurements of the oxidation state of vanadium in diesel vehicle PM emissions. The emission rates and the measured fraction of V(V) in PM from diesel engines running without exhaust after-treatment were both low (2-3 ng/mile and 13-16%, respectively). The V(IV) species was measured as the dominant vanadium species in diesel PM emissions. A significantly greater fraction of V(V) (76%) was measured in PM from the engine fitted with a prototype vanadium-based selective catalytic reductors (V-SCR) retrofit. The emission rate of V(V) determined for the V-SCR equipped vehicle (103 ng/mile) was 40-fold greater than that from the baseline vehicle. A clear contrast between the PM size-distributions of V(V) and V(IV) emissions was apparent, with the V(V) distribution characterized by a major single mode in the ultrafine (<0.25 μm) size range and the V(IV) size distribution either flat or with a small maxima in the accumulation mode (0.5-2 μm). The V(V) content of the V-SCR PM (6.6 μg/g) was 400-fold greater than that in PM from baseline (0.016 μg/g) vehicles, and among the highest of all environmental samples examined. Synchrotron

  3. One year online chemical speciation of submicron particulate matter (PM1) sampled at a French industrial and coastal site

    NASA Astrophysics Data System (ADS)

    Zhang, Shouwen; Riffault, Véronique; Dusanter, Sébastien; Augustin, Patrick; Fourmentin, Marc; Delbarre, Hervé

    2015-04-01

    The harbor of Dunkirk (Northern France) is surrounded by different industrial plants (metallurgy, petrochemistry, food processing, power plant, etc.), which emit gaseous and particulate pollutants such as Volatile Organic Compounds (VOCs), oxides of nitrogen (NOx) and sulfur (SO2), and submicron particles (PM1). These emissions are poorly characterized and their impact on neighboring urban areas has yet to be assessed. Studies are particularly needed in this type of complex environments to get a better understanding of PM1sources, especially from the industrial sector, their temporal variability, and their transformation. Several instruments, capable of real-time measurements (temporal resolution ≤ 30 min), were deployed at a site located downwind from the industrial area of Dunkirk for a one-year duration (July 2013-September 2014). An Aerosol Chemical Speciation Monitor (ACSM) and an Aethalometer monitored the main chemical species in the non-refractory submicron particles and black carbon, respectively. Concomitant measurements of trace gases and wind speed and direction were also performed. This dataset was analyzed considering four wind sectors, characteristics of marine, industrial, industrial-urban, and urban influences, and the different seasons. We will present a descriptive analysis of PM1, showing strong variations of ambient concentrations, as well as evidences of SO2 to SO4 gas-particle conversion when industrial plumes reached the monitoring site. The organic fraction measured by ACSM (37% of the total mass on average) was analyzed using a source-receptor model based on Positive Matrix Factorization (PMF) to identify chemical signatures of main emission sources and to quantify the contribution of each source to the PM1 budget given the wind sector. Four main factors were identified: hydrocarbon organic aerosol (HOA), oxygenated organic aerosol (OOA), biomass burning organic aerosol (BBOA) and cooking-like organic aerosol (COA). Overall, the total PM

  4. Comparison of Aerosol Mass Spectrometer and Aerosol Chemical Speciation Monitor Measurements of Secondary Organic Aerosol Formation in Smog Chamber Studies

    NASA Astrophysics Data System (ADS)

    Croteau, P. L.; Hunter, J. F.; Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Canagaratna, M.; Jayne, J.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Thermal vaporization-electron impact ionization (TV-EI) mass spectrometry is a powerful tool for understanding the chemistry of secondary organic aerosol (SOA) formation and atmospheric aging. The Aerodyne Aerosol Mass Spectrometer (AMS) and recently developed Aerosol Chemical Speciation Monitor (ACSM) are two instruments that utilize the same TV-EI technique. The ACSM trades the particle sizing capability, sensitivity, speed, and resolution of the AMS for simplicity, affordability, and ease of operation - enabling stand-alone continuous sampling for extended periods of time. Here we present results of an intercomparison between a high-resolution AMS and an ACSM. Three well-studied SOA formation chamber experiments were conducted: isoprene photooxidation under high NOx conditions, m-xylene photooxidation under high NOx conditions, and α-pinene ozonolysis under low NOx conditions. Comparisons between time-series and mass spectra from these experiments, along with positive matrix factorization analysis results demonstrate that the ACSM, while it does not provide the same level of detail as an AMS, is a suitable tool for exploring the chemistry of SOA formation in chamber studies.

  5. Fine particulate matter source apportionment for the chemical speciation trends network site at Birmingham, Alabama, using positive matrix factorization

    SciTech Connect

    Baumann, K.; Jayanty, R.K.; Flanagan, J.B.

    2008-01-15

    The Positive Matrix Factorization (PMF) receptor model version 1.1 was used with data from the fine particulate matter (PM2.5) Chemical Speciation Trends Network (STN) to estimate source contributions to ambient PM2.5 in a highly industrialized urban setting in the southeastern United States. Model results consistently resolved 10 factors that are interpreted as two secondary, five industrial, one motor vehicle, one road dust, and one biomass burning sources. It was found that most PMF factors did not cleanly represent single source types and instead are 'contaminated' by other sources. Secondary particulate matter formed by atmospheric processes, such as sulfate and secondary OC, contribute the majority of ambient PM2.5 and exhibit strong seasonality 37 {+-} 10% winter vs. 55 {+-} 16% summer average. Motor vehicle emissions constitute the biggest primary PM2.5 mass contribution. In summary, this study demonstrates the utility of the EC tracer method to effectively blank-correct the OC concentrations in the STN dataset. In addition, examination of the effect of input uncertainty estimates on model results indicates that the estimated uncertainties currently being provided with the STN data may be somewhat lower than the levels needed for optimum modeling results. An appendix , available to members on the website www.awma lists stationary sources of PM2.5 within 10 km of the NHBM site and PM2.5 emissions greater than 1 ton per year. 71 refs., 7 figs., 9 tabs.

  6. Laboratory Study of Chemical Speciation of Mercury in Lake Sediment and Water under Aerobic and Anaerobic Conditions

    PubMed Central

    Regnell, Olof; Tunlid, Anders

    1991-01-01

    Chemical speciation and partitioning of radiolabeled HgCl2 were studied in model aquatic systems consisting of undisturbed eutrophic lake sediment and water in plastic cylinders. The cylinders were either gradually made anaerobic by a gentle flow of N2-CO2 or kept aerobic by air flow. The proportion of methylated 203Hg was significantly higher, in both water and sediment, in the anaerobic systems than in the aerobic systems. The composition and total concentration of fatty acids originating from bacterial phospholipids, as well as the concentration of vitamin B12, including related cobalamins, were similar in sediments from the anaerobic and aerobic systems. Bacterial cell numbers were, on average, 3.6 times higher in the anaerobic water columns than in the aerobic ones. Volatilization of 203Hg occurred in all systems except in an autoclaved control and was of similar magnitudes in the anaerobic and aerobic systems. Incorporation of 203Hg into the sediment was significantly faster in the aerobic systems than in the anaerobic systems. These results suggest that episodes of anoxia in bottom waters and sediment cause an increase in net mercury methylation and, hence, an increase in bioavailable mercury. PMID:16348444

  7. Chemical speciation and leaching properties of elements in municipal incinerator ashes

    SciTech Connect

    Kida, Akiko; Noma, Yukio; Imada, Teruji

    1996-12-31

    Different chemical properties of bottom ash and fly ash from municipal solid waste incinerators were compared based on the results of the five measuring techniques: (1) total contents and leaching amounts by regulatory leaching test in Japan; (2) leaching properties by pH-dependent leaching test; (3) modeling of pH-dependent leaching test using model compounds; (4) enriched chemical composition compared with bulk composition by an X-ray photoelectron spectrometer (XPS); (5) estimation of chemical states of elements by XPS analysis. The difference between bottom ash and EP ash was clearly found in element content, leaching behavior and release rate. The release rates of many elements in bottom ash were lower than in electrostatic precipitation (EP) ash even in an acidic condition of pH 3 as well as at the inherent pH of 12. Corresponding to the relatively complicated components in bottom ash, leaching patterns depending on pH were not simple. Comparison between the pH-dependent pattern of Ca in a sample and in model compounds resulted in the estimation of some Ca compounds in ash. The surface analysis by XPS showed results that Na, Cl, Zn, Pb and S were enriched in EP ash and Fe and Ti were rarely found in the surface of ash. Possible chemical states of Na, Ca, K, Cl and S were estimated by a new method of comparing binding energies of standard compounds and their mixtures.

  8. Chemical speciation of polyurethane polymers by soft-x-ray spectromicroscopy

    SciTech Connect

    Rightor, E.G.; Hitchcock, A.P.; Urquhart, S.G.

    1997-04-01

    Polyurethane polymers are a versatile class of materials which have numerous applications in modern life, from automotive body panels, to insulation, to household furnishings. Phase segregation helps to determine the physical properties of several types of polyurethanes. Polymer scientists believe that understanding the connections between formulation chemistry, the chemical nature of the segregated phases, and the physical properties of the resulting polymer, would greatly advance development of improved polyurethane materials. However, the sub-micron size of segregated features precludes their chemical analysis by existing methods, leaving only indirect means of characterizing these features. For the past several years the authors have been developing near edge X-ray absorption spectromicroscopy to study the chemical nature of individual segregated phases. Part of this work has involved studies of molecular analogues and model polymers, in conjunction with quantum calculations, in order to identify the characteristic near edge spectral transitions of important chemical groups. This spectroscopic base is allowing the authors to study phase segregation in polyurethanes by taking advantage of several unique capabilities of scanning transmission x-ray microscopy (STXM) - high spatial resolution ({approximately} 0.1 {mu}m), high spectral resolution ({approximately}0.1 eV at the C 1s edge), and the ability to record images and spectra with relatively low radiation damage. The beamline 7.0 STXM at ALS is being used to study microtomed sections or cast films of polyurethanes. Based on the pioneering work of Ade, Kirz and collaborators at the NSLS X-1A STXM, it is clear that scanning X-ray transmission microscopy using soft X-rays can provide information about the chemical origin of phase segregation in radiation-sensitive materials on a sub-micron scale. This information is difficult or impossible to obtain by other means.

  9. Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in Downtown Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

    2013-12-01

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was recently developed to provide long-term real-time continuous measurements of ambient non-refractory (i.e., organic, sulfate, ammonium, nitrate, and chloride) submicron particulate matter (NR-PM1). Currently, there are a limited number of field studies that evaluate the long-term performance of the ACSM against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. The collocated measurements included a second ACSM, continuous and integrated sulfate, nitrate, and ammonium measurements, as well as a semi-continuous Sunset organic carbon/elemental carbon (OC/EC) analyzer, continuous tapered element oscillating microbalance (TEOM), 24 h integrated Federal Reference Method (FRM) filters, and continuous scanning electrical mobility system-mixing condensation particle counter (SEMS-MCPC). Intercomparison of the two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21); mass concentration for all chemical species agreed within ±27%, indicating that ACSM instruments are capable of stable and reproducible operation. Chemical constituents measured by the ACSM are also compared with those obtained from the continuous measurements from JST. Since the continuous measurement concentrations are adjusted to match the integrated filter measurements, these comparisons reflect the combined uncertainties of the ACSM, continuous, and filter measurements. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Differences between ACSM mass concentrations and the filter-adjusted JST continuous data are 5-27%, 4

  10. Chemical Speciation of Sulfur in Marine Cloud Droplets and Particles: 1. Analysis of Individual Particles Using Complementary Microprobe Methods.

    NASA Astrophysics Data System (ADS)

    Desyaterik, Y.; Hopkins, R. J.; Tivanski, A. V.; Berkowitz, C. M.; Gilles, M. K.; Laskin, A.

    2006-12-01

    Chemical speciation of dry residues of individual cloud droplets and interstitial aerosol collected from sea-fog during the Marine Stratus Experiment (MASE) in July 2005 was facilitated using a complementary combination of computer controlled scanning electron microscopy with energy dispersed analysis of x-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOF-SIMS), and scanning transmission x-ray microscopy with near edge x-ray absorption fine structure spectroscopy (STXM/NEXAFS). Particle samples were collected at the ground site located in Pt. Reyes National Seashore, about 0.5 miles from the ocean coast over the period of time when the air plume, that originated over the open ocean, passed the area of the cold stream along the northern California coast. Based on composition, morphology, and microstructure, two externally mixed, distinct types of sea-fog particles were identified in the samples: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate excessive formation of methanesulfonate (CH3SO3-) rather then non-sea-salt sulfate (nss-SO42-) in the sea salt particles. This observation is consistent with the recent modeling studies of dimethylsulfide (DMS) oxidation chemistry in the marine boundary layer (MDL). Modeling studies predict enhanced formation of CH3SO3- in activated sea salt particles under cloudy MBL conditions over the areas with low ocean surface temperatures. We discuss the climate related effects of this chemistry which likely results in: a) increasing size and hygroscopicity of the pre-existing CCN (sea salt particles), and b) reducing the production of gaseous H2SO4 and subsequent new sulfate particle formation.

  11. Extraction of Chemical Speciation and Molar Absorption Coeficients with Well-posed Solutions of Beer's Law

    SciTech Connect

    Boily, Jean F.; Suleimenov, Oleg M.

    2006-06-01

    The ability of two different approaches in retrieving thermodynamic and spectroscopic properties of chemical species, using Beer’s law, was investigated on a suite of synthetic uv-vis spectra generated at various degrees of random error. Analytical and numerical solutions to direct solutions to Beer’s law were compared to solutions starting from orthogonalised absorbance matrices filtered from random noise by the method of Singular Value Decomposition. Solutions making use of absorbance matrices filtered from random noise were the most successful at retrieving properties of chemical species at larger errors. Repeated automated simulation however indicated such solutions to display a number of occurrences associated to poor fits to the synthetic data while direct solutions to Beer’s law produced more consistent sets of values. A bootstrap statistical analysis of the repeated simulations showed the median quality of the fit (e.g. sum-of-squares of the deviations) to be nonetheless far superior for solutions making use of error/noise filtration than those of direct solutions to Beer’s law. These former solutions are therefore recommended for the extraction of spectroscopic and thermodynamic/kinetic properties of chemical species from spectroscopic data, however not without a rigorous validation of the model.

  12. Speciation and chemical evolution of nitrogen oxides in aircraft exhaust near airports.

    PubMed

    Wood, Ezra C; Herndon, Scott C; Timko, Michael T; Yelvington, Paul E; Miake-Lye, Richard C

    2008-03-15

    Measurements of nitrogen oxides from a variety of commercial aircraft engines as part of the JETS-APEX2 and APEX3 campaigns show that NOx (NOx [triple bond] NO + NO2) is emitted primarily in the form of NO2 at idle thrust and NO at high thrust. A chemical kinetics combustion model reproduces the observed NO2 and NOx trends with engine power and sheds light on the relevant chemical mechanisms. Experimental evidence is presented of rapid conversion of NO to NO2 in the exhaust plume from engines at low thrust. The rapid conversion and the high NO2/NOx emission ratios observed are unrelated to ozone chemistry. NO2 emissions from a CFM56-3B1 engine account for approximately 25% of the NOx emitted below 3000 feet (916 m) and 50% of NOx emitted below 500 feet (153 m) during a standard ICAO (International Civil Aviation Organization) landing-takeoff cycle. Nitrous acid (HONO) accounts for 0.5% to 7% of NOy emissions from aircraft exhaust depending on thrust and engine type. Implications for photochemistry near airports resulting from aircraft emissions are discussed.

  13. Chemical speciation and source apportionment of fine particulate matter in Santiago, Chile, 2013.

    PubMed

    Villalobos, Ana M; Barraza, Francisco; Jorquera, Héctor; Schauer, James J

    2015-04-15

    Santiago is one of the largest cities in South America and has experienced high fine particulate matter (PM2.5) concentrations in fall and winter months for decades. To better understand the sources of fall and wintertime pollution in Santiago, PM2.5 samples were collected for 24 h every weekday from March to October 2013 for chemical analysis. Samples were analyzed for mass, elemental carbon (EC), organic carbon (OC), water soluble organic carbon (WSOC), water soluble nitrogen (WSTN), secondary inorganic ions, and particle-phase organic tracers for source apportionment. Selected samples were analyzed as monthly composites for organic tracers. PM2.5 concentrations were considerably higher in the coldest months (June-July), averaging (mean ± standard deviation) 62±15 μg/m(3) in these two months. Average fine particle mass concentration during the study period was 40±20 μg/m(3). Organic matter during the peak winter months was the major component of fine particles comprising around 70% of the particle mass. Source contributions to OC were calculated using organic molecular markers and a chemical mass balance (CMB) receptor model. The four combustion sources identified were wood smoke, diesel engine emission, gasoline vehicles, and natural gas. Wood smoke was the predominant source of OC, accounting for 58±42% of OC in fall and winter. Wood smoke and nitrate were the major contributors to PM2.5. In fall and winter, wood smoke accounted for 9.8±7.1 μg/m(3) (21±15%) and nitrate accounted for 9.1±4.8 μg/m(3) (20±10%) of fine PM. The sum of secondary inorganic ions (sulfate, nitrate, and ammonium) represented about 30% of PM2.5 mass. Secondary organic aerosols contributed only in warm months, accounting for about 30% of fine PM during this time. PMID:25617780

  14. Chemical speciation and source apportionment of fine particulate matter in Santiago, Chile, 2013.

    PubMed

    Villalobos, Ana M; Barraza, Francisco; Jorquera, Héctor; Schauer, James J

    2015-04-15

    Santiago is one of the largest cities in South America and has experienced high fine particulate matter (PM2.5) concentrations in fall and winter months for decades. To better understand the sources of fall and wintertime pollution in Santiago, PM2.5 samples were collected for 24 h every weekday from March to October 2013 for chemical analysis. Samples were analyzed for mass, elemental carbon (EC), organic carbon (OC), water soluble organic carbon (WSOC), water soluble nitrogen (WSTN), secondary inorganic ions, and particle-phase organic tracers for source apportionment. Selected samples were analyzed as monthly composites for organic tracers. PM2.5 concentrations were considerably higher in the coldest months (June-July), averaging (mean ± standard deviation) 62±15 μg/m(3) in these two months. Average fine particle mass concentration during the study period was 40±20 μg/m(3). Organic matter during the peak winter months was the major component of fine particles comprising around 70% of the particle mass. Source contributions to OC were calculated using organic molecular markers and a chemical mass balance (CMB) receptor model. The four combustion sources identified were wood smoke, diesel engine emission, gasoline vehicles, and natural gas. Wood smoke was the predominant source of OC, accounting for 58±42% of OC in fall and winter. Wood smoke and nitrate were the major contributors to PM2.5. In fall and winter, wood smoke accounted for 9.8±7.1 μg/m(3) (21±15%) and nitrate accounted for 9.1±4.8 μg/m(3) (20±10%) of fine PM. The sum of secondary inorganic ions (sulfate, nitrate, and ammonium) represented about 30% of PM2.5 mass. Secondary organic aerosols contributed only in warm months, accounting for about 30% of fine PM during this time.

  15. Chemical speciation of chromium(III) and (VI) using phosphonium cation impregnated polyurethane foams prior to their spectrometric determination.

    PubMed

    El-Shahawi, M S; Bashammakh, A S; Abdelmageed, M

    2011-01-01

    Fast and selective sorptions of Cr(VI) species from aqueous media onto tetraphenylphosphonium bromide (TPP(+) · Br(-)) physically immobilized polyurethane foams (PUFs) sorbent were achieved. Based on the Scatchard model of binding sites of the PUFs and Langmuir and Dubinin-Radushkevich (D-R) adsorption models of Cr(VI) retention onto TPP(+) · Br(-) immobilized PUFs, a dual retention mechanism involving absorption related to "weak-base anion ion exchange" and an added component for "surface adsorption" was proposed. Thus, the TPP(+) · Br(-) loaded PUFs were successfully packed in column mode for preconcentration of trace and ultra trace concentrations of Cr(VI) as halochromates [CrO(3)C](-)(aq) from aqueous HCl media. The retained [CrOCl(3)](-)(aq) species were recovered with NaOH (1.0 mol L(-1)) and analyzed by flame atomic absorption spectrometry. Cr(III) species after oxidation to Cr(VI) with H(2)O(2) in aqueous KOH (1.0 mol L(-1)) were also retained and could be recovered by the proposed method. The limits of detection (LOD) and quantification (LOQ) of Cr(VI) were 0.04 and 0.13 µg L(-1), respectively. The chemical speciation of Cr(III, VI) species in various water samples at trace and ultra trace levels were carried out by TPP(+) · Br(-) loaded PUFs packed column. The enhancement factor and sensitivity factor of [CrO(3)C](-)(aq) sorption were 80.0 and 30.0, respectively. PMID:21747186

  16. Distribution and chemical speciation of arsenic in ancient human hair using synchrotron radiation.

    PubMed

    Kakoulli, Ioanna; Prikhodko, Sergey V; Fischer, Christian; Cilluffo, Marianne; Uribe, Mauricio; Bechtel, Hans A; Fakra, Sirine C; Marcus, Matthew A

    2014-01-01

    Pre-Columbian populations that inhabited the Tarapacá mid river valley in the Atacama Desert in Chile during the Middle Horizon and Late Intermediate Period (AD 500-1450) show patterns of chronic poisoning due to exposure to geogenic arsenic. Exposure of these people to arsenic was assessed using synchrotron-based elemental X-ray fluorescence mapping, X-ray absorption spectroscopy, X-ray diffraction and Fourier transform infrared spectromicroscopy measurements on ancient human hair. These combined techniques of high sensitivity and specificity enabled the discrimination between endogenous and exogenous processes that has been an analytical challenge for archeological studies and criminal investigations in which hair is used as a proxy of premortem metabolism. The high concentration of arsenic mainly in the form of inorganic As(III) and As(V) detected in the hair suggests chronic arsenicism through ingestion of As-polluted water rather than external contamination by the deposition of heavy metals due to metallophilic soil microbes or diffusion of arsenic from the soil. A decrease in arsenic concentration from the proximal to the distal end of the hair shaft analyzed may indicate a change in the diet due to mobility, though chemical or microbiologically induced processes during burial cannot be entirely ruled out. PMID:24320096

  17. Distribution and chemical speciation of arsenic in ancient human hair using synchrotron radiation.

    PubMed

    Kakoulli, Ioanna; Prikhodko, Sergey V; Fischer, Christian; Cilluffo, Marianne; Uribe, Mauricio; Bechtel, Hans A; Fakra, Sirine C; Marcus, Matthew A

    2014-01-01

    Pre-Columbian populations that inhabited the Tarapacá mid river valley in the Atacama Desert in Chile during the Middle Horizon and Late Intermediate Period (AD 500-1450) show patterns of chronic poisoning due to exposure to geogenic arsenic. Exposure of these people to arsenic was assessed using synchrotron-based elemental X-ray fluorescence mapping, X-ray absorption spectroscopy, X-ray diffraction and Fourier transform infrared spectromicroscopy measurements on ancient human hair. These combined techniques of high sensitivity and specificity enabled the discrimination between endogenous and exogenous processes that has been an analytical challenge for archeological studies and criminal investigations in which hair is used as a proxy of premortem metabolism. The high concentration of arsenic mainly in the form of inorganic As(III) and As(V) detected in the hair suggests chronic arsenicism through ingestion of As-polluted water rather than external contamination by the deposition of heavy metals due to metallophilic soil microbes or diffusion of arsenic from the soil. A decrease in arsenic concentration from the proximal to the distal end of the hair shaft analyzed may indicate a change in the diet due to mobility, though chemical or microbiologically induced processes during burial cannot be entirely ruled out.

  18. Chemical Speciation and Bioaccessibility of Arsenic and Chromiumin Chromated Copper Arsenate-Treated Wood and Soils

    SciTech Connect

    Nico, Peter S.; Ruby, Michael V.; Lowney, Yvette W.; Holm,Stewart E.

    2005-10-12

    This research compares the As and Cr chemistry ofdislodgeable residues from Chromated Copper Arsenate (CCA)-treated woodcollected by two different techniques (directly from the board surfaceeither by rubbing with a soft bristle brush or from human hands aftercontact with CCA-treated wood), and demonstrates that these materials areequivalent in terms of the chemical form and bonding of As and Cr and interms of the As leaching behavior. This finding links the extensivechemical characterization and bioavailability testing that has been donepreviously on the brush-removed residue to a material that is derivedfrom human skin contact with CCA-treated wood. Additionally, thisresearch characterizes the arsenic present in biological fluids (sweatand simulated gastric fluid) following contact with these residues. Thedata demonstrate that in biological fluids, the arsenic is presentprimarily as free arsenate ions.Arsenic-containing soils were alsoextracted into human sweat to evaluate the potential for arsenicdissolution from soils at the skin surface. For soils from field sites,only a small fraction of the total arsenic is soluble in sweat. Based oncomparisons to reference materials that have been used in in vivo dermalabsorption studies, these findings suggest that the actual relativebioavailability via dermal absorption of As from CCA-residues and soilmay be well below the current default value of 3 percent used by U.S.EPA.

  19. 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.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

    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

  20. Chemical speciation of redox sensitive elements during hydrocarbon leaching in the Junggar Basin, Northwest China

    NASA Astrophysics Data System (ADS)

    Zheng, Guodong; Fu, Bihong; Takahashi, Yoshio; Kuno, Akihito; Matsuo, Motoyuki; Zhang, Jindong

    2010-11-01

    Bleaching related to seepage of petroleum fluids and subsurface migration of crude oil and natural gas can alter the chemical and mineralogical properties of rocks, while concurrently depleting hydrocarbon reservoirs. Mud volcanoes constitute one type of petroleum seepage present in several areas on the southern margin of the Junggar Basin in the Xinjiang Uygur Autonomous Region, NW China. The results of XRD, XRF, XANES, and Mössbauer spectroscopy on rock samples collected from areas affected by these mud volcanoes revealed an enrichment of certain minerals and elements, as well changes in mineralogical, molecular, or ionic carrier ("species"). After bleaching, reddish sedimentary rocks showed depletion in silica and enrichment of calcium, magnesium, manganese, and iron. Other elements, including aluminum, potassium, sodium, and titanium, were largely unchanged. Reduced iron and sulfur compounds predominated in the bleached rocks, producing changes in color from the original reddish into green, deep gray, and black. Iron and calcium were associated with carbonates, indicating carbonation of these elements during the bleaching processes. Manganese also appeared to be associated with carbonate, though not with sulfate even though sulfate was present in the bleached rocks. Alkaline conditions were apparently the dominant because reduced manganese would have been absent under acidic condition. The alteration of certain minerals, clay minerals in particular, was also observed in bleached rocks, the alteration of smectite-group minerals to chlorite and muscovite, for example. Mineralogical and geochemical changes in rocks bleached by hydrocarbon fluids could provide a better overall understanding of bleaching processes, and may have applications in surface geochemical exploitation and remote imaging.

  1. 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.

  2. Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water

    NASA Astrophysics Data System (ADS)

    Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A.; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F. Javier; Alvarez-Puebla, Ramon A.

    2014-06-01

    Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels

  3. Chemical speciation in mining affected waters: the case study of Asarel-Medet mine.

    PubMed

    Rabadjieva, Diana; Tepavitcharova, Stefka; Todorov, Tihomir; Dassenakis, Manos; Paraskevopoulou, Vasiliki; Petrov, Mihail

    2009-12-01

    The inorganic chemical species in Maresh and Luda Yana rivers affected by the Cu- Mo Asarel-Medet mine, Bulgaria were determined during a low-flow and a high-flow period. The mining activities, the weathering and the oxidation processes strongly influenced the physicochemical processes in the whole water system. The main pollution source was a small lake receiving the acid effluents of the mining activities. High levels of SO4(2-), Cu, Mg, Al, Mn and Fe were determined at the mining polluted and affected stations. Cu(2+) and CuCO3(0) species (1:1) were present in the reference waters and Cu(2+) and CuSO4(0) species (1:1) in the polluted and affected waters; Cu(2+) species was dominating downstream. Me(2+) followed by MeSO4(0) (Me = Mn, Zn, Cd and Pb), PbCO3(0) and PbHCO3(+) species as well as Fe(OH)2(+), Al(OH)4(-), Al(OH)2(+), Al(OH)3(0) were prevailing in the system. MeSO4(+) and Me(SO4)2(-) (Me = Fe, Al), Me(SO4)2(2-) (Me = Zn, Cd and Pb), Me(SO4)3(4-) (Me = Zn, Cd) and Cd(SO4)4(6-) species polluted and affected waters. The major elements K and Na were mainly Me(+) species, whereas Ca and Mg were Me(2+) and MeSO4(0) species in different ratios. The concentration of concentration of NO2(-), NO3(-) and NO4(+) species as well as complex phosphorous species such as H2PO4(-), FeHPO4(+), HPO4(2-), CaPO4(-), CaHPO4(0) and MgHPO4(0) were also calculated. The trace element concentrations decreased downstream due to dilution, sorption processes and precipitation, but the percentage of free metal species, which are more toxic, increased. An exception was iron and aluminum of which the dominant hydroxy colloidal and sulphate species were easily incorporated into the suspended phase.

  4. Levels and chemical speciation of arsenic in representative biota and sediments of a tropical mangrove wetland, India.

    PubMed

    Fattorini, Daniele; Sarkar, Santosh Kumar; Regoli, Francesco; Bhattacharya, Bhaskar Deb; Rakshit, Dibyendu; Satpathy, Kamala Kanta; Chatterjee, Mousumi

    2013-04-01

    The general concern for arsenic in the marine environment is associated with its wide distribution and potential toxicity. In the present work, concentrations and chemical speciation of arsenic were characterized in sediments and representative biota from the Indian Sundarban, the largest continuous mangrove tract formed at the mouth of the Hugli (Ganges) River estuary, northeastern part of the Bay of Bengal. Analyzed organisms included both shellfish (Macoma birmanica, Sanguinolaria acuminata and Meretrix meretrix) and finfish (Liza parsia, Liza tade, Harpodon nehereus and Eleutheronema tetradactylum). Arsenic concentrations in sediments did not exceed 4 μg g(-1) dry weight with the contribution of inorganic molecules (arsenate and arsenite) ranging from 61.7 to 81.3%. Total As (TAs) concentrations varied from less than 2 to 16 μg g(-1) in tissues of bivalves; the more elevated As accumulation was observed in gills and the mantle probably due to ion exchange properties of the mucous layer covering these organs, whereas adductor muscle and the podium showed limited values. Distribution of various arsenic compounds followed a quite similar trend in bivalve tissues; arsenobetaine (AsB) was the most dominant form followed by compounds such as dimethylarsinate (DMA), trimethyl arsine-oxide (TMAO), tetramethyl arsonium (TETRA) and arsenocholine (AsC), while inorganic arsenic (IAs) represented a minor constituent (0.2 to 6.9%). Among the fish, detritivorous/herbivorous species (L. parsia and L. tade) exhibited TAs concentrations of 10.8 and 9.71 μg g(-1) dry wt with a prevalence of AsB (52-67%) and TETRA (26-35%); higher concentrations of TAs were measured in the two carnivorous species (20.62 and 19.67 μg g(-1) dry wt, in H. nehereus and E. tetradactylum respectively) mostly as AsB (63.3-72.3%) and AsC (17.5-28.6%). The obtained results can be considered as baseline levels for arsenic in the investigated area, confirming the predominance of organoarsenicals in

  5. Indian emissions of technology-linked NMVOCs with chemical speciation: An evaluation of the SAPRC99 mechanism with WRF-CAMx simulations

    NASA Astrophysics Data System (ADS)

    Sarkar, M.; Venkataraman, C.; Guttikunda, S.; Sadavarte, P.

    2016-06-01

    Non-methane volatile organic compounds (NMVOCs) are important precursors to reactions producing tropospheric ozone and secondary organic aerosols. The present work uses a detailed technology-linked NMVOC emission database for India, along with a standard mapping method to measured NMVOC profiles, to develop speciated NMVOC emissions, which are aggregated into multiple chemical mechanisms used in chemical transport models. The fully speciated NMVOC emissions inventory with 423 constituent species, was regrouped into model-ready reactivity classes of the RADM2, SAPRC99 and CB-IV chemical mechanisms, and spatially distributed at 25 × 25 km2 resolution, using source-specific spatial proxies. Emissions were considered from four major sectors, i.e. industry, transport, agriculture and residential and from non-combustion activities (use of solvents and paints). It was found that residential cooking with biomass fuels, followed by agricultural residue burning in fields and on-road transport, were largest contributors to the highest reactivity group of NMVOC emissions from India. The emissions were evaluated using WRF-CAMx simulations, using the SAPRC99 photochemical mechanism, over India for contrasting months of April, July and October 2010. Modelled columnar abundance of NO2, CO and O3 agreed well with satellite observations both in magnitude and spatial distribution, in the three contrasting months. Evaluation of monthly and spatial differences between model predictions and observations indicates the need for further refinement of the spatial distribution of NOX emissions, spatio-temporal distribution of agricultural residue burning emissions.

  6. Indian emissions of technology-linked NMVOCs with chemical speciation: An evaluation of the SAPRC99 mechanism with WRF-CAMx simulations

    NASA Astrophysics Data System (ADS)

    Sarkar, M.; Venkataraman, C.; Guttikunda, S.; Sadavarte, P.

    2016-06-01

    Non-methane volatile organic compounds (NMVOCs) are important precursors to reactions producing tropospheric ozone and secondary organic aerosols. The present work uses a detailed technology-linked NMVOC emission database for India, along with a standard mapping method to measured NMVOC profiles, to develop speciated NMVOC emissions, which are aggregated into multiple chemical mechanisms used in chemical transport models. The fully speciated NMVOC emissions inventory with 423 constituent species, was regrouped into model-ready reactivity classes of the RADM2, SAPRC99 and CB-IV chemical mechanisms, and spatially distributed at 25 × 25 km2 resolution, using source-specific spatial proxies. Emissions were considered from four major sectors, i.e. industry, transport, agriculture and residential and from non-combustion activities (use of solvents and paints). It was found that residential cooking with biomass fuels, followed by agricultural residue burning in fields and on-road transport, were largest contributors to the highest reactivity group of NMVOC emissions from India. The emissions were evaluated using WRF-CAMx simulations, using the SAPRC99 photochemical mechanism, over India for contrasting months of April, July and October 2010. Modelled columnar abundance of NO2, CO and O3 agreed well with satellite observations both in magnitude and spatial distribution, in the three contrasting months. Evaluation of monthly and spatial differences between model predictions and observations indicates the need for further refinement of the spatial distribution of NOX emissions, spatio-temporal distribution of agricultural residue burning emissions.

  7. Computer modelling of the chemical speciation of caesium, uranium(VI) and neptunium(V) in human duodenal fluids under fasting conditions.

    PubMed

    Jones, Paul W; Taylor, David M; Webb, Louise M; Williams, David R

    2002-08-01

    A model simulating the human duodenal contents under physiologically realistic, fasting conditions was developed using the joint expert speciation system (JESS) computer program and database and used to investigate the chemical speciation of caesium, uranium(VI) and neptunium(V). Over the pH range 5.0-9.0, and the concentration range 5 x 10(-15) x 10(-5) mol dm(-3), caesium was predicted to occur predominantly as the absorbable free monovalent cation Cs+ (approximately 95%) with species such as CsHPO4- and CsCl representing the remainder. The presence or absence of sulphate at 2.1 x 10(-3) mol dm(-3) did not influence the predicted speciation. Uranium was predicted to be present entirely as a soluble, highly charged species, both in the absence and in the presence of sulphate. Between pH 5.0 and approximately 6.5 the UO2H2(PO4)2(2-) predominated, above this pH carbonate species, either UO2(CO3)4(6-) or, possibly, UO2(CO3)5(8-). At pH 8.0, and in the presence of sulphate, neptunium(V) was predicted to exist solely as the tetrasulphate species, whilst in the absence of sulphate, an array of negatively charged soluble carbonate species predominated. Studies over the pH range 5.0-9.0 predicted the formation of a spectrum of negatively charged carbonate and phosphate species, approximately 40% of the total neptunium was predicted to be present as the electrically net-neutral species NpO2HCO3 at pH6.0, approximately 20% at pH 7.0, approximately 10% at pH 7.5 and approximately 1% at pH 8.0. The observed speciation patterns of uranium and neptunium did not change over the concentration range 5 x 10(-15) - 5 x 10(-5) mol dm(-3) and no solid species were predicted to occur under the conditions simulated. Whether the predicted electrically net-neutral neptunium species or the uranium pentacarbonate species do actually occur under true physiological conditions remains to be established. The observed speciation patterns for caesium and uranium are consistent with the observed

  8. Determination of zinc speciation in basic oxygen furnace flying dust by chemical extractions and X-ray spectroscopy.

    PubMed

    Sammut, M L; Rose, J; Masion, A; Fiani, E; Depoux, M; Ziebel, A; Hazemann, J L; Proux, O; Borschneck, D; Noack, Y

    2008-02-01

    There is a growing concern regarding the environmental and public health risks associated with airborne particulate matter (PM). The basic oxygen furnace is one of the most important atmospheric dust sources of the steel manufacturing process. It emits dust enriched in heavy metal such as Zn, which is assumed to contribute to the toxic potential of atmospheric PM. Dust collected before and after the filtration system was analyzed to determine Zn speciation. To this end, a variety of analytical tools were used and a sequential extraction protocol has been specifically developed for iron and steel dust. The Zn speciation results obtained by EXAFS and sequential extraction were in excellent agreement. Before filtration, the speciation of Zn in BOF was 43% ZnFe(2)O(4), 23% ZnCO(3) and 16% ZnO. The same species were detected after filtration with different proportions. BOF dust after filtration contains more soluble Zn phases which may play a role in the toxic effects of the emissions.

  9. Distribution of Cd, Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

    NASA Astrophysics Data System (ADS)

    Du, Ping; Xue, Nandong; Liu, Li; Li, Fasheng

    2008-07-01

    An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40-80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.

  10. Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards.

    PubMed

    Lathouri, Maria; Korre, Anna

    2015-12-15

    Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals. Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality

  11. Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards.

    PubMed

    Lathouri, Maria; Korre, Anna

    2015-12-15

    Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals. Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality

  12. Identification of the chemical form of sulfur compounds in the Japanese pink coral (Corallium elatius) skeleton using μ-XRF/XAS speciation mapping.

    PubMed

    Tamenori, Yusuke; Yoshimura, Toshihiro; Luan, Nguyen Trong; Hasegawa, Hiroshi; Suzuki, Atsushi; Kawahata, Hodaka; Iwasaki, Nozomu

    2014-05-01

    The distributions and chemical forms of sulfur compounds in the skeleton of Japanese pink coral (Corallium elatius) were investigated using X-ray spectroscopic techniques combined with micro-focused soft X-ray radiation. Microscopic X-ray fluorescence/soft X-ray photoabsorption (μ-XRF/XAS) speciation mapping clarified that sulfate is the primary species in the coral skeleton, with minor amounts of organic sulfur, whereas both sulfate and organic sulfur coexist in coenenchyme. Analysis of the post-edge region of the XAS spectra confirmed that sulfate ions in the coral skeleton are mainly in the form of gypsum-like inorganic sulfate substituting for the carbonate ions in the calcite skeleton. The sulfate concentration was negatively correlated with the magnesium concentration and positively correlated with that of phosphorus. Speciation mapping of sulfate in the coral skeleton showed clear fluctuations with sulfate concentrations being higher at dark bands, whereas the small amount of organic sulfur had unclear dark/bright bands. These results suggest that the little organic sulfur that is present is contained in the organic matter embedded in the biocrystal of coral skeleton.

  13. Special Speciation

    ERIC Educational Resources Information Center

    Countryman, Lyn L.; Maroo, Jill D.

    2015-01-01

    Considerable anecdotal evidence indicates that some of the most difficult concepts that both high school and undergraduate elementary-education students struggle with are those surrounding evolutionary principles, especially speciation. It's no wonder that entry-level biology students are confused, when biologists have multiple definitions of…

  14. Chemical speciation of Fe and Ni in residual oil fly ash fine particulate matter using X-ray absorption spectroscopy.

    PubMed

    Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

    2012-12-01

    Epidemiological studies have linked residual oil fly ash fine particulate matter with aerodynamic diameter <2.5 μm (ROFA PM(2.5)) to morbidity and mortality from cardiovascular and respiratory illnesses. Bioavailable transition metals within PM have been cited as one of the components that induce such illnesses. By combining synchrotron-based X-ray absorption spectroscopy with leaching experiment, we studied the effect of residual oil compositions and combustion conditions on the speciation of Fe and Ni in ROFA PM(2.5) and the implication of these species for human health and environment. PM(2.5) samples were obtained from two types of combustors, a fire tube boiler (FTB) and a refractory line combustor (RLC). The study reveals that only Fe(2)(SO(4))(3)·nH(2)O is present in RLC PM(2.5) while Fe(2)(SO(4))(3)·nH(2)O predominates in FTB PM(2.5) with inclusion of varying amounts of nickel ferrite. The finding that RLC PM(2.5) is more bioavailable and hence more toxic than FTB PM(2.5) is significant. The reduction of toxicity of FTB PM(2.5) is due to the immobilization of a portion of Fe and Ni in the formation of an insoluble NiFe(2)O(4). This may explain the variation of toxicity from exposure to different ROFA PM(2.5). Additionally, the speciation data are sought for developing emission inventories for source apportionment study and understanding the mechanism of PM formation.

  15. Chemical Speciation of Sulfur in Marine Cloud Droplets and Particles: Analysis of Individual Particles from Marine Boundary Layer over the California Current

    SciTech Connect

    William R. Wiley Environmental Sciences Laboratory, Pacific Northwest National Laboratory; Gilles, Mary K; Hopkins, Rebecca J.; Desyaterik, Yury; Tivanski, Alexei V.; Zaveri, Rahul A.; Berkowitz, Carl M.; Tyliszczak, Tolek; Gilles, Mary K.; Laskin, Alexander

    2008-03-12

    Detailed chemical speciation of the dry residue particles from individual cloud droplets and interstitial aerosol collected during the Marine Stratus Experiment (MASE) was performed using a combination of complementary microanalysis techniques. Techniques include computer controlled scanning electron microscopy with energy dispersed analysis of X-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOF-SIMS), and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Samples were collected at the ground site located in Point Reyes National Seashore, approximately 1 km from the coast. This manuscript focuses on the analysis of individual particles sampled from air masses that originated over the open ocean and then passed through the area of the California current located along the northern California coast. Based on composition, morphology, and chemical bonding information, two externally mixed, distinct classes of sulfur containing particles were identified: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate substantial heterogeneous replacement of chloride by methanesulfonate (CH3SO3-) and non-sea salt sulfate (nss-SO42-) in sea-salt particles with characteristic ratios of nss-S/Na>0.10 and CH3SO3-/nss-SO42->0.6.

  16. A new paradigm for constraining PM2.5 speciation by combining multiangular and polarimetric remote sensing with chemical transport model information

    NASA Astrophysics Data System (ADS)

    Kalashnikova, O.; Xu, F.; Ge, C.; Wang, J.; Garay, M. J.; Diner, D. J.

    2014-12-01

    Exposure to ambient particulate matter (PM) has been consistently linked to cardiovascular and respiratory health effects. Although PM is currently monitored by a network of surface stations, these are too sparsely distributed to provide the level of spatial detail needed to link different aerosol species to given health effects, and expansion to denser coverage is impractical and cost prohibitive. We present a methodology for combining Chemical Transport Model (CTM) aerosol type information and multiangular spectropolarimetric data to establish the signature of specific aerosol types in top-of-atmosphere measurements, and relate it to speciated surface PM2.5 loadings. In particular, we employ the WRF-Chem model run at the University of Nebraska, and remote sensing data from the Airborne Multiangle SpectroPolarimetric Imager (AirMSPI) to explore the feasibility of this approach. We demonstrate that the CTM does well in predicting the types of aerosols present at a given location and time, however large uncertainties currently exist in CTM estimates of the concentration of the various aerosol species (e.g., black carbon, sulfate, dust, etc.) leading to large uncertainties to model-derived speciated PM 2.5. In order to constrain CTM aerosol surface concentrations we use AirMSPI UV-VIS-NIR observations of intensity, and blue, red, and NIR observations of the Q and U Stokes parameters. We select specific scenes observed by AirMSPI and use WRF-Chem to generate an initial distribution of aerosol composition. The relevant optical properties for each aerosol species are used to calculate aerosol light scattering information. This is then used in a vector (polarized) 1-D radiative transfer model to determine at-instrument Stokes parameters for the specific AirMSPI viewing geometries. As a first step, a match is sought between the CTM-predicted radiances and the AirMSPI observations. Then, the total aerosol optical depth and fractions of various aerosol species are modified

  17. Speciation and bioavailability of dissolved copper in different freshwaters: comparison of modelling, biological and chemical responses in aquatic mosses and gammarids.

    PubMed

    Bourgeault, Adeline; Ciffroy, Philippe; Garnier, Cédric; Cossu-Leguille, Carole; Masfaraud, Jean-François; Charlatchka, Rayna; Garnier, Jean-Marie

    2013-05-01

    Biological and chemical measurements were performed in mesocosms to investigate the bioavailability of copper, with a greater emphasis on the effects of competing ions and copper speciation. Measurements were achieved in three different natural waters for two aquatic species (Gammarus pulex and Fontinalis antipyretica) along a copper gradient concentration: natural concentration, spiked at 5 and 15 μg L(-1). Aquatic mosses exhibited high enrichment rates that were above the background levels compared to gammarids. The accumulation of copper in F. antipyretica is better correlated to the weakly complexed copper concentrations measured using differential pulse anodic stripping voltammetry (DPASV) and diffusive gradient in thin film (DGT) than to the free copper concentration measured using an ion selective electrode (ISE). In unspiked natural waters, the presence of dissolved organic ligands strongly controls the metal speciation and consequently largely minimised the impact of competing cations on the accumulation of Cu in mosses. Furthermore, the BioMet Biotic Ligand Model (BLM) successfully describes the site-specific copper bioaccumulation for the freshwater mosses studied. However, the comparison of the results with a previous study appears to indicate that the adsorption/desorption of Cu in mosses is impacted by seasons. This highlights a limit of the BioMet model in which the physiological state of aquatic organisms is not considered. No toxic effect of Cu exposure on lipid peroxidation was observed in the mosses and gammarids regardless of the site and the concentration considered. However, the oxidative stress measured in the mosses via their guaiacol peroxidase (GPX) activity increased in the case where internalised Cu reached maximal values, which suggests a threshold effect on the GPX activity.

  18. Speciation and bioavailability of dissolved copper in different freshwaters: comparison of modelling, biological and chemical responses in aquatic mosses and gammarids.

    PubMed

    Bourgeault, Adeline; Ciffroy, Philippe; Garnier, Cédric; Cossu-Leguille, Carole; Masfaraud, Jean-François; Charlatchka, Rayna; Garnier, Jean-Marie

    2013-05-01

    Biological and chemical measurements were performed in mesocosms to investigate the bioavailability of copper, with a greater emphasis on the effects of competing ions and copper speciation. Measurements were achieved in three different natural waters for two aquatic species (Gammarus pulex and Fontinalis antipyretica) along a copper gradient concentration: natural concentration, spiked at 5 and 15 μg L(-1). Aquatic mosses exhibited high enrichment rates that were above the background levels compared to gammarids. The accumulation of copper in F. antipyretica is better correlated to the weakly complexed copper concentrations measured using differential pulse anodic stripping voltammetry (DPASV) and diffusive gradient in thin film (DGT) than to the free copper concentration measured using an ion selective electrode (ISE). In unspiked natural waters, the presence of dissolved organic ligands strongly controls the metal speciation and consequently largely minimised the impact of competing cations on the accumulation of Cu in mosses. Furthermore, the BioMet Biotic Ligand Model (BLM) successfully describes the site-specific copper bioaccumulation for the freshwater mosses studied. However, the comparison of the results with a previous study appears to indicate that the adsorption/desorption of Cu in mosses is impacted by seasons. This highlights a limit of the BioMet model in which the physiological state of aquatic organisms is not considered. No toxic effect of Cu exposure on lipid peroxidation was observed in the mosses and gammarids regardless of the site and the concentration considered. However, the oxidative stress measured in the mosses via their guaiacol peroxidase (GPX) activity increased in the case where internalised Cu reached maximal values, which suggests a threshold effect on the GPX activity. PMID:23500400

  19. Atmospheric mercury concentration and chemical speciation at a rural site in Beijing, China: implication of mercury emission sources

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Wang, S. X.; Wang, L.; Hao, J. M.

    2013-05-01

    Continuous measurements of atmospheric mercury concentration and speciation play a key role in identifying mercury sources and its behavior in the atmosphere. In this study, speciated atmospheric mercury including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) were continuously measured at Miyun, a rural site in Beijing, China from December 2008 to November 2009. The average GEM, RGM and PBM concentrations were found to be 3.22 ± 1.74 ng m-3, 10.1 ± 18.8 pg m-3 and 98.2 ± 112.7 pg m-3, respectively, about 2-20 times of the background concentration of Northern Hemisphere. The results indicated that atmospheric mercury concentrations in North China were highly affected by anthropogenic emissions. The atmospheric mercury showed obvious seasonal variations with the highest seasonal average GEM concentration in summer (3.48 ng m-3) and the lowest value in winter (2.66 ng m-3). In autumn and winter a diurnal variation of GEM was observed with peak levels in late afternoon till midnight. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher oxidation. The PBM concentration was higher in early morning of all seasons because of the atmospheric stratification during nighttime against laminar fluxes during daytime. The ratio of GEM to CO indicates that residential boilers play an important role in the elevation of GEM in winter. The ratio of RGM to O3 could be an indicator of the contribution of local primary sources. The ratio of PBM to PM2.5 reveals that the air mass from east and southwest to the site in spring and summer carries more atmospheric mercury. The HYSPLIT back-trajectory analysis indicated that the monitoring site is affected by local, regional and interregional sources simultaneously during heavy pollution episodes. The results from the potential source contribution function (PSCF) model indicate that the atmospheric transport predominantly from the northwest

  20. Atmospheric mercury concentration and chemical speciation at a rural site in Beijing, China: implications of mercury emission sources

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Wang, S. X.; Wang, L.; Hao, J. M.

    2013-10-01

    Continuous measurements of atmospheric mercury concentration and speciation play a key role in identifying mercury sources and its behavior in the atmosphere. In this study, speciated atmospheric mercury including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) were continuously measured at Miyun, a rural site in Beijing, China, from December 2008 to November 2009. The average GEM, RGM and PBM concentrations were found to be 3.22 ± 1.74, 10.1 ± 18.8 and 98.2 ± 112.7 pg m-3, respectively, about 2-20 times higher than the background concentration of the Northern Hemisphere. The results indicated that atmospheric mercury concentrations in northern China were highly affected by anthropogenic emissions. The atmospheric mercury showed obvious seasonal variations, with the highest seasonal average GEM concentration in summer (3.48 ng m-3) and the lowest value in winter (2.66 ng m-3). In autumn and winter a diurnal variation of GEM was observed, with peak levels in the late afternoon till midnight. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher oxidation. The PBM concentration was higher in early morning of all seasons because of the the temperature inversion that increases in depth as the night proceeds. The ratio of GEM to CO indicates that residential boilers play an important role in the elevation of GEM in winter. The ratio of RGM to O3 could be an indicator of the contribution of local primary sources. The ratio of PBM to PM2.5 reveals that the air mass from the east and southwest of the site in spring and summer carries more atmospheric mercury. The HYSPLIT back-trajectory analysis indicated that the monitoring site is affected by local, regional and interregional sources simultaneously during heavy pollution episodes. The results from the potential source contribution function (PSCF) model indicate that the atmospheric transport predominantly from the northwest

  1. Chemical speciation and ecological risk assessment of arsenic in marine sediments from Izmir Bay (Eastern Aegean Sea).

    PubMed

    Gonul, L T

    2015-12-01

    Total arsenic, arsenic(III) and (V), Fe, and Mn were measured in 17 surface sediment samples from Izmir Bay. The concentrations and ecological risk of As were characterized in the sediment affected by urban and agricultural activities. Total As ranged from 8.87 to 28.3 μg g(-1) dry weight (96.5-99.9 % as inorganic As). Distribution of total As and total As/Fe followed a different trend in sediments at all sampling sites. Arsenite (As(III)) was the most dominant form followed by As(V), while organic arsenic represented a minor constituent (0.03 to 3.49 %). The highest concentration of total As was observed at Gediz River estuary and exceeded lower threshold value (threshold effects level (TEL)). Due to the biological reduction of As(V) and abundance of Fe (oxyhydr)oxides in the sediments, most inorganic As in the Izmir Bay was present as As(III). Besides, the levels of As were >TEL and speciation analysis to accurately assess potential toxicity of marine resources and provides a crucial baseline to assess the impact of future development within this region.

  2. Vapor pressure, speciation, and chemical activities in highly concentrated sodium borate solutions at 277 and 317{degrees}C

    SciTech Connect

    Weres, O.

    1995-05-01

    The system H{sub 2}O - B{sub 2}O{sub 3} - Na{sub 2}O has been studied experimentally at 277 and 317{degrees}C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 8 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modeled using the Pitzer-Simonson model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. The potassium borate system also was briefly studied at 317{degrees}C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B = 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.

  3. 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.

  4. Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS).

    PubMed

    Brittain, S R; Cox, A G; Tomos, A D; Paterson, E; Siripinyanond, A; McLeod, C W

    2012-03-01

    Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied. PMID:22237634

  5. 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. PMID:26898203

  6. Emission inventory of primary pollutants and chemical speciation in 2010 for the Yangtze River Delta region, China

    NASA Astrophysics Data System (ADS)

    Fu, Xiao; Wang, Shuxiao; Zhao, Bin; Xing, Jia; Cheng, Zhen; Liu, Huan; Hao, Jiming

    2013-05-01

    We developed a high-resolution emission inventory of primary air pollutants for Yangtze River Delta (YRD) region, which included Shanghai plus 24 cities in the provinces of Jiangsu and Zhejiang. The emissions of SO2, NOX, PM10, PM2.5, NMVOCs and NH3 in the year of 2010 were estimated as 2147 kt, 2776 kt, 1006 kt, 643 kt, 3822 kt and 1439 kt, respectively. Power plants are the largest emission sources for SO2 and NOX, which contributes 44.1% and 37.3% of total SO2 and NOX emissions. Emissions from industrial process accounted for 26.9%, 28.9% and 33.7% of the total PM10, PM2.5 and NMVOCs respectively. Besides, 37.3% of NMVOCs emissions were contributed by solvent use. Livestock and fertilizer application contribute over 90% of NH3 emissions. High emission densities are visible in Shanghai and the area around Tai Lake. This emission inventory includes the speciation of PM2.5 for the YRD region for the first time, which is important to source apportionment and secondary-pollution analysis. In 2010, emissions of three major PM2.5 species, namely OC, EC and sulfate, are 136.9 kt, 75.0 kt and 76.2 kt, respectively. Aromatics and alkanes are the main NMVOC species, accounting for 30.4% and 20.3% of total VOCs. Non-road transportation and biomass burning were main uncertain sources because of a lack of proper activity and emission factor data. Compared with other pollutants, NMVOCs and NH3 have higher uncertainty. From 2000 to 2010, emissions of all pollutants have changed significantly, suggesting that the newly updated and high-resolution emission inventory will be useful for the identification of air pollution sources in YRD.

  7. Relating metal exposure and chemical speciation to trace metal accumulation in aquatic insects under natural field conditions.

    PubMed

    De Jonge, Maarten; Lofts, Stephen; Bervoets, Lieven; Blust, Ronny

    2014-10-15

    The present study investigated to what extent measured dissolved metal concentrations, WHAM-predicted free metal ion activity and modulating water chemistry factors can predict Ni, Cu, Zn, Cd and Pb accumulation in various aquatic insects under natural field conditions. Total dissolved concentrations and accumulated metal levels in four taxa (Leuctra sp., Simuliidae, Rhithrogena sp. and Perlodidae) were determined and free metal ion activities were calculated in 36 headwater streams located in the north-west part of England. Observed invertebrate body burdens were strongly related to free metal ion activities and competition among cations for uptake in the biota. Taking into account competitive effects generally provided better fits than considering uptake as a function of total dissolved metal levels or the free ion alone. Due to the critical importance and large range in pH (4.09 to 8.33), the H(+) ion activity was the most dominant factor influencing metal accumulation. Adding the influence of Na(+) on Cu(2+) accumulation improved the model goodness of fit for both Rhithrogena sp. and Perlodidae. Effects of hardness ions on metal accumulation were limited, indicating the minor influence of Ca(2+) and Mg(2+) on metal accumulation in soft-water streams (0.01 to 0.94 mM Ca; 0.02 to 0.39 mM Mg). DOC levels (ranging from 0.6 to 8.9 mg L(-1)) significantly affected Cu body burdens, however not the accumulation of the other metals. Our results suggest that 1) uptake and accumulation of free metal ions are most dominantly influenced by competition of free H(+) ions in low-hardness headwaters and 2) invertebrate body burdens in natural waters can be predicted based on the free metal ion activity using speciation modelling and effects of H(+) competition.

  8. Soluble organic carbon and pH of organic amendments affect metal mobility and chemical speciation in mine soils.

    PubMed

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

    2014-05-01

    We evaluated the effects of pH and soluble organic carbon affected by organic amendments on metal mobility to find out the optimal conditions for their application in the stabilization of metals in mine soils. Soil samples (pH 5.5-6.2) were mixed with 0, 30 and 60 th a(-1) of sheep-horse manure (pH 9.4) and pine bark compost (pH 5.7). A single-step extraction procedure was performed using 0.005 M CaCl2 adjusted to pH 4.0-7.0 and metal speciation in soil solution was simulated using NICA-Donnan model. Sheep-horse manure reduced exchangeable metal concentrations (up to 71% Cu, 75% Zn) due to its high pH and degree of maturity, whereas pine bark increased them (32% Cu, 33% Zn). However, at increasing dose and hence pH, sheep-horse manure increased soluble Cu because of higher soluble organic carbon, whereas soluble Cu and organic carbon increased at increasing dose and correspondingly decreasing pH in pine bark and non-amended treatments. Near the native pH of these soils (at pH 5.8-6.3), with small doses of amendments, there was minimum soluble Cu and organic carbon. Pine bark also increased Zn solubility, whereas sheep-horse manure reduced it as soluble Zn always decreased with increasing pH. Sheep-horse manure also reduced the proportion of free metals in soil solution (from 41% to 4% Cu, from 97% to 94% Zn), which are considered to be more bioavailable than organic species. Sheep-horse manure amendment could be efficiently used for the stabilization of metals with low risk of leaching to groundwater at low doses and at relatively low pH, such as the native pH of mine soils.

  9. Speciation analysis of mercury in cereals by liquid chromatography chemical vapor generation inductively coupled plasma-mass spectrometry.

    PubMed

    Lin, Liang-Yen; Chang, Lan-Fang; Jiang, Shiuh-Jen

    2008-08-27

    A simple and rapid procedure for the separation and determination of inorganic, methyl, and ethyl mercury compounds was described using liquid chromatography (LC) followed by vapor generation inductively coupled plasma-mass spectrometry (VG-ICP-MS). Well resolved chromatograms were obtained within 5 min by reversed-phase liquid chromatography with a C8 column as the stationary phase and a pH 4.7 solution containing 0.5% v/v 2-mercaptoethanol and 5% v/v methanol as the mobile phase. The separated mercury compounds were converted to mercury vapors by an in situ nebulizer/vapor generation system for their introduction into ICP. The concentrations of NaBH4 and HNO3 required for vapor generation were also optimized. The method was applied for the speciation of mercury in reference materials NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour and also rice flour and wheat flour samples purchased locally. The accuracy of the procedure was verified by analyzing the certified reference material NRCC DOLT-3 Dogfish Liver for methyl mercury. Precision between sample replicates was better than 13% for all the determinations. The detection limits of the mercury compounds studied were in the range 0.003-0.006 ng Hg mL(-1) in the injected solutions, which correspond to 0.02-0.06 ng g(-1) in original flour samples. A microwave-assisted extraction procedure was adopted for the extraction of mercury compounds from rice flour, wheat flour, and fish samples using a mobile phase solution.

  10. Relating metal exposure and chemical speciation to trace metal accumulation in aquatic insects under natural field conditions.

    PubMed

    De Jonge, Maarten; Lofts, Stephen; Bervoets, Lieven; Blust, Ronny

    2014-10-15

    The present study investigated to what extent measured dissolved metal concentrations, WHAM-predicted free metal ion activity and modulating water chemistry factors can predict Ni, Cu, Zn, Cd and Pb accumulation in various aquatic insects under natural field conditions. Total dissolved concentrations and accumulated metal levels in four taxa (Leuctra sp., Simuliidae, Rhithrogena sp. and Perlodidae) were determined and free metal ion activities were calculated in 36 headwater streams located in the north-west part of England. Observed invertebrate body burdens were strongly related to free metal ion activities and competition among cations for uptake in the biota. Taking into account competitive effects generally provided better fits than considering uptake as a function of total dissolved metal levels or the free ion alone. Due to the critical importance and large range in pH (4.09 to 8.33), the H(+) ion activity was the most dominant factor influencing metal accumulation. Adding the influence of Na(+) on Cu(2+) accumulation improved the model goodness of fit for both Rhithrogena sp. and Perlodidae. Effects of hardness ions on metal accumulation were limited, indicating the minor influence of Ca(2+) and Mg(2+) on metal accumulation in soft-water streams (0.01 to 0.94 mM Ca; 0.02 to 0.39 mM Mg). DOC levels (ranging from 0.6 to 8.9 mg L(-1)) significantly affected Cu body burdens, however not the accumulation of the other metals. Our results suggest that 1) uptake and accumulation of free metal ions are most dominantly influenced by competition of free H(+) ions in low-hardness headwaters and 2) invertebrate body burdens in natural waters can be predicted based on the free metal ion activity using speciation modelling and effects of H(+) competition. PMID:25051425

  11. Trace metal speciation in natural waters: Computational vs. analytical

    USGS Publications Warehouse

    Kirk, Nordstrom D.

    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

  12. Submicron-Chemical Speciation of Late Albian, Well-Preserved Fossil Samples from Tlayúa, the Mexican Solenhofen.

    NASA Astrophysics Data System (ADS)

    Marcus, M.; Fakra, S.; Tamura, N.; Alvarado-Ortega, J.; Espinosa-Arruberena, L.; Banfield, J.; Cervini-Silva, J.

    2007-12-01

    brackish and freshwater environments. In search for reconstructing paleoenvironments in Tlayúa, fish bone samples from a Pachyrhizodontide specimens, from the telesteos incertae sedis group already extinct, were analyzed using XRFmicro X-ray fluorescence,  -X-ray diffraction RD, and -EXAFSnd XANES/EXAFS. Conducting Ca- EXAFS allowed us to resolve Ca-speciation in CaCO3 matrices. Micro Ca-EXAFSDiffraction and Ca K-edge XANES on bone material confirmed the presence of apatite, not hydroxyapatite consistent with highly-weathered environment. High concentrations of As were found in CaCO3) grains, Mn oxides grains as well as Celestine (SrSO4) grains dispersed in the egg core.

  13. Assessment of the toxicity of metals in soils amended with sewage sludge using a chemical speciation technique and a lux-based biosensor

    SciTech Connect

    McGrath, S.P.; Knight, B.; Killham, K.; Preston, S.; Paton, G.I.

    1999-04-01

    Currently, regulations regarding the maximum permitted concentrations of metals in soils are based on measurements of the total concentration. However, a range of chemical and biological techniques are being developed to predict the bioavailable component of these pollutants. A lux-based biosensor was tested in soil solutions extracted from two field experiments at Braunschweig, Germany, that had the same metal inputs, but differed in pH. The bioluminescence response was found to decline as the free Zn{sup 2+} increased, and both soils fitted the same relationship with soil solution metal concentrations. The EC25 and EC50 derived from this curve were 1.9 and 6.1 mg/L, respectively. In contrast, the response to total Zn concentrations in the bulk soil showed distinct curves for each soil, further highlighting the appropriateness of free Zn{sup 2+} as a toxicity indicator. Other metals were present in the soil, but were unlikely to be toxic, because the observed concentrations were less than their individual toxic threshold values in solution. Bioluminescence-based biosensors were concluded to possibly offer an inexpensive and rapid technique to evaluate the bioavailability of metals in soil systems. The response of these biosensors can be related to soil solution speciation measurements, and this gives a common basis for expression of toxic thresholds in different soils.

  14. Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy.

    PubMed

    Sakata, Kohei; Sakaguchi, Aya; Tanimizu, Masaharu; Takaku, Yuichi; Yokoyama, Yuka; Takahashi, Yoshio

    2014-02-01

    Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima (Japan) have been determined by X-ray absorption near-edge structure (XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3 Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.

  15. Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

    NASA Astrophysics Data System (ADS)

    Sun, C.; Lee, B. P.; Huang, D.; Jie Li, Y.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

    2016-02-01

    Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

  16. Continuous measurements at the urban roadside in an Asian Megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

    NASA Astrophysics Data System (ADS)

    Sun, C.; Lee, B. P.; Huang, D.; Li, Y. J.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

    2015-07-01

    Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 at the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear meal-time concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during meal times, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a~lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and influence of continental air masses.

  17. Chemical speciation of Fe, Mn, Pb, Zn, Cd, Cu, Co, Ni and Cr in the suspended particulate matter off the Mejerda River Delta (Gulf of Tunis, Tunisia)

    NASA Astrophysics Data System (ADS)

    Helali, Mohamed Amine; Oueslati, Walid; Zaaboub, Noureddine; Added, Ayed; Aleya, Lotfi

    2016-06-01

    Fluxes of suspended particulate matter (SPM) and their associated metals were performed off the Mejerda River Delta during both the wet (March) and the dry (July) seasons in 2012, using sediment traps at study stations at depths of 10, 20 and 40 m. Fluxes nearest to the Mejerda outlet were more significant, especially during winter (36 g m-2 day-1), but dissipated further offshore, 24.5-6 g m-2 day-1 at the 20 m and 21.8-4.8 g m-2 day-1 at the 40 m stations. Many variations observed in seasonal and spatial metal fluxes are similar to those of SPM, in particular Pb and Zn, probably because they are associated with the mining activity characteristic of the Mejerda catchment. Chemical speciation reveals that most of the metals (20-100%) are bound to the residual fraction. The most toxic metals (Pb, Zn) are bound in part to the exchangeable fraction (20-50% for Pb and 5-15% for Zn) making them relatively bioavailable and therefore potentially toxic. While Cu and Cd fluxes are not always clearly established according to season, both metals are apparently sequestered deep in the sediment, bound especially to clays (40-80% for Cd and up to 100% for Cu).

  18. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    NASA Astrophysics Data System (ADS)

    Parworth, Caroline; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Tilp, Alison; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ∼30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations of the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  19. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    SciTech Connect

    Parworth, Caroline; Tilp, Alison; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations of the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  20. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    DOE PAGES

    Parworth, Caroline; Tilp, Alison; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations ofmore » the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.« less

  1. Non-refractory PM1 in SE Asia: Chemically speciated aerosol fluxes and concentrations above contrasting land-uses in SE Asia.

    NASA Astrophysics Data System (ADS)

    Phillips, Gavin; Farmer, Delphine; di Marco, Chiara; Misztal, Pawel; Sueper, Donna; Kimmel, Joel; Jimenez, Jose; Fowler, David; Nemitz, Eiko

    2010-05-01

    New measurements of VOC emissions (measured with leaf cuvettes, and ecosystem fluxes obtained from eddy covariance measurements) suggest that oil palm (Elaeis guineensis Jacq) is a significantly larger source of isoprene than tropical forest, in Borneo. These larger sources of isoprene measured over oil palm, allied with a larger anthropogenic component of local emissions, contrasts with the composition of the atmosphere in the semi-remote tropical forest environment. The difference in the atmospheric composition above different land-uses has the potential to lead to contrasting chemistry and physics controlling the formation and processing of particulate matter. Thus land use changes, driven by the economics of biofuels, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions, chemical processing and composition of organic aerosol over both (semi-)natural and anthropogenic land uses in the tropical environment. Ecosystem flux measurements of chemically-speciated non-refractory PM1 were made over two contrasting land uses in the Malaysian state of Sabah, on the island of Borneo during 2008. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at the Global Atmospheric Watch (GAW) site at a tropical rain forest location as well as the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as a collaboration between three UK NERC funded projects (OP3, APPRAISE/ACES and DIASPORA). Recent technical developments using ToF detectors allow us to record 10 Hz full mass spectra at both high resolution (HR) and unit-mass resolution (UMR), suitable for the calculation of local eddy-covariance fluxes. The measurements provide information on the deposition rate of anthropogenic aerosol components (e.g. sulphate, nitrate, ammonium and hydrocarbon-like aerosol) to tropical forest and oil palm. At the same time, any biogenic secondary organic

  2. Chemical speciation of size-segregated floor dusts and airborne magnetic particles collected at underground subway stations in Seoul, Korea.

    PubMed

    Jung, Hae-Jin; Kim, BoWha; Malek, Md Abdul; Koo, Yong Sung; Jung, Jong Hoon; Son, Youn-Suk; Kim, Jo-Chun; Kim, HyeKyoung; Ro, Chul-Un

    2012-04-30

    Previous studies have reported the major chemical species of underground subway particles to be Fe-containing species that are generated from wear and friction processes at rail-wheel-brake and catenaries-pantographs interfaces. To examine chemical composition of Fe-containing particles in more details, floor dusts were collected at five sampling locations of an underground subway station. Size-segregated floor dusts were separated into magnetic and non-magnetic fractions using a permanent magnet. Using X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), iron metal, which is relatively harmless, was found to be the dominating chemical species in the floor dusts of the <25 μm size fractions with minor fractions of Mg, Al, Si, Ca, S, and C. From SEM analysis, the floor dusts of the <25 μm size fractions collected on railroad ties appeared to be smaller than 10 μm, indicating that their characteristics should somewhat reflect the characteristics of airborne particles in the tunnel and the platform. As most floor dusts are magnetic, PM levels at underground subway stations can be controlled by removing magnetic indoor particles using magnets. In addition, airborne subway particles, most of which were smaller than 10 μm, were collected using permanent magnets at two underground subway stations, namely Jegi and Yangjae stations, in Seoul, Korea. XRD and SEM/EDX analyses showed that most of the magnetic aerosol particles collected at Jegi station was iron metal, whereas those at Yangjae station contained a small amount of Fe mixed with Na, Mg, Al, Si, S, Ca, and C. The difference in composition of the Fe-containing particles between the two subway stations was attributed to the different ballast tracks used. PMID:22381374

  3. Chemical speciation of size-segregated floor dusts and airborne magnetic particles collected at underground subway stations in Seoul, Korea.

    PubMed

    Jung, Hae-Jin; Kim, BoWha; Malek, Md Abdul; Koo, Yong Sung; Jung, Jong Hoon; Son, Youn-Suk; Kim, Jo-Chun; Kim, HyeKyoung; Ro, Chul-Un

    2012-04-30

    Previous studies have reported the major chemical species of underground subway particles to be Fe-containing species that are generated from wear and friction processes at rail-wheel-brake and catenaries-pantographs interfaces. To examine chemical composition of Fe-containing particles in more details, floor dusts were collected at five sampling locations of an underground subway station. Size-segregated floor dusts were separated into magnetic and non-magnetic fractions using a permanent magnet. Using X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), iron metal, which is relatively harmless, was found to be the dominating chemical species in the floor dusts of the <25 μm size fractions with minor fractions of Mg, Al, Si, Ca, S, and C. From SEM analysis, the floor dusts of the <25 μm size fractions collected on railroad ties appeared to be smaller than 10 μm, indicating that their characteristics should somewhat reflect the characteristics of airborne particles in the tunnel and the platform. As most floor dusts are magnetic, PM levels at underground subway stations can be controlled by removing magnetic indoor particles using magnets. In addition, airborne subway particles, most of which were smaller than 10 μm, were collected using permanent magnets at two underground subway stations, namely Jegi and Yangjae stations, in Seoul, Korea. XRD and SEM/EDX analyses showed that most of the magnetic aerosol particles collected at Jegi station was iron metal, whereas those at Yangjae station contained a small amount of Fe mixed with Na, Mg, Al, Si, S, Ca, and C. The difference in composition of the Fe-containing particles between the two subway stations was attributed to the different ballast tracks used.

  4. Long-term Measurements of Submicrometer Aerosol Chemistry at the Southern Great Plains (SGP) Using an Aerosol Chemical Speciation Monitor (ACSM)

    SciTech Connect

    Parworth, Caroline; Fast, Jerome D.; Mei, Fan; Shippert, Timothy R.; Sivaraman, Chitra; Tilp, Alison; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the U.S. Department of Energy’s Southern Great Plains (SGP) site are discussed. Over the period of 19 months (Nov. 20, 2010 – June 2012) highly time resolved (~30 min.) NR-PM1 data was recorded. Using this dataset the value-added product (VAP) of deriving organic aerosol components (OACOMP) is introduced. With this VAP, multivariate analysis of the measured organic mass spectral matrix can be performed on long term data to return organic aerosol (OA) factors that are associated with distinct sources, evolution processes, and physiochemical properties. Three factors were obtained from this VAP including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when nitrate increased due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations showed little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increased and were mainly associated with local fires. Isoprene and carbon monoxide emission rates were computed by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) to represent the spatial distribution of biogenic and anthropogenic sources, respectively. From this model there is evidence to support that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  5. Seasonal and spatial variation of trace elements in multi-size airborne particulate matters of Beijing, China: Mass concentration, enrichment characteristics, source apportionment, chemical speciation and bioavailability

    NASA Astrophysics Data System (ADS)

    Gao, Jiajia; Tian, Hezhong; Cheng, Ke; Lu, Long; Wang, Yuxuan; Wu, Ye; Zhu, Chuanyong; Liu, Kaiyun; Zhou, Junrui; Liu, Xingang; Chen, Jing; Hao, Jiming

    2014-12-01

    The seasonal and spatial variation characteristics of 19 elements (Al, As, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, S, Sb, Se, Zn) in TSP/PM10/PM2.5 samples were investigated, which were collected from April 2011 to January 2012 simultaneously at an urban downtown site, a traffic roadside site, a suburban site, and a rural site in Beijing. The elevated concentrations of several toxic trace elements (As, Cd, Mn, Ni, Pb, etc.) in particles revealed that the contamination of toxic elements in Beijing could not be neglected. Positive matrix factorization method (PMF) was applied for source apportionment of trace elements in PM, and three factors (crust related sources, combustion sources, and traffic and steel industrial related sources) were identified. Furthermore, the chemical speciation and bioavailability of various elements were identified by applying European Community Bureau of Reference (BCR) procedure. Our results showed that eight toxic elements (As, Cd, Cr, Cu, Ni, Pb, Sb and Zn) exhibited higher mobility in PM2.5 than in PM10. Notably, elements of As, Cd, Pb and Zn were presented with higher mobility than the other elements, and these elements were lightly to release into the environment and easily available to human body. Additionally, As, Cd, Pb and Zn also accounted for higher percentages in the bound to mobile fractions at the central urban areas of Beijing. Therefore, special concerns should be paid to these toxic trace elements which had relatively high mobility in fine particles, when planning and implementing the comprehensive air pollution mitigation policies in Beijing.

  6. Non-chromatographic speciation analysis of mercury by flow injection on-line preconcentration in combination with chemical vapor generation atomic fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Wu, Hong; Jin, Yan; Han, Weiying; Miao, Qiang; Bi, Shuping

    2006-07-01

    A novel non-chromatographic approach for direct speciation of mercury, based on the selective retention inorganic mercury and methylmercury on the inner wall of a knotted reactor by using ammonium diethyl dithiophosphate and dithizone as complexing agents respectively, was developed for flow injection on-line sorption preconcentration coupled with chemical vapor generation non-dispersive atomic fluorescence spectrometry. With the sample pH kept at 2.0, the preconcentration of inorganic mercury on the inner walls of the knotted reactor was carried out based on the exclusive retention of Hg-DDP complex in the presence of methylmercury via on-line merging the sample solution with ammonium diethyl dithiophosphate solution, and selective preconcentration methylmercury was achieved with dithizone instead of ammonium diethyl dithiophosphate. A 15% (v/v) HCl was introduced to elute the retained mercury species and merge with KBH 4 solution for atomic fluorescence spectrometry detection. Under the optimal experimental conditions, the sample throughputs of inorganic mercury and methylmercury were 30 and 20 h - 1 with the enhancement factors of 13 and 24. The detection limits were found to be 3.6 ng l - 1 for Hg 2+ and 2.0 ng l - 1 for CH 3Hg +. The precisions (RSD) for the 11 replicate measurements of each 0.2 μg l - 1 of Hg 2+ and CH 3Hg + were 2.2% and 2.8%, respectively. The developed method was validated by the analysis of certified reference materials (simulated natural water, rice flour and pork) and by recovery measurements on spiked samples, and was applied to the determination of inorganic mercury and methylmercury in biological and environmental water samples.

  7. Impacts of chemical amendment and plant growth on lead speciation and enzyme activities in a shooting range soil: an x-ray absorption fine structure investigation.

    PubMed

    Hashimoto, Yohey; Matsufuru, Hiroki; Takaoka, Masaki; Tanida, Hajime; Sato, Takeshi

    2009-01-01

    In situ chemical immobilization is a practical remediation technology for metal-contaminated soils because of its capability to reduce cost and environmental impacts. We assessed the immobilization effects of poultry waste amendment and plant growth (Panicum maximum Jacq.) on Pb speciation and enzyme activities in shooting range soils. Soil contaminated with Pb was obtained from the top 20 cm of a shooting range. To evaluate Pb mobility in the soil profile treated with plants and immobilizing amendment, we used large columns filled with Pb-contaminated soil (0-20 cm, surface soils) and non-contaminated soil (20-75 cm, subsurface soils). The column study demonstrated that the amendment reduced the toxicity characteristic leaching procedure-extractable Pb in the surface soil by 90% of the Control soil. Lead mobility from the surface to subsurface profiles was significantly attenuated by plant growth but was promoted by the amendment without plant application. The extended X-ray absorption fine structure analysis revealed that the amendment reduced the proportion of PbCO(3) and Pb-organic complexes and transformed them into a more geochemically stable species of Pb(5)(PO(4))(3)Cl with 30 to 35% of the total Pb species. Applications of plant and amendment increased activities of dehydrogenase and phosphatase in the surface soil with 2.7- and 1.1-fold greater than those in Control, respectively. The use of amendments in combination with plant growth may have potential as an integrated remediation strategy that enables Pb immobilization and soil biological restoration in shooting range soils.

  8. Environmental applications of XANES: Speciation of {Tc} in cement after chemical treatment and Se after bacterial uptake

    SciTech Connect

    Shuh, D.K.; Kaltsoyannis, N.; Bucher, J.J.

    1994-03-01

    XANES (X-ray Absorption Near Edge Spectroscopy) has been employed to evaluate the efficacy of a process designed to encapsulate and reduce {Tc}O{sub 4}{sup {minus}} in cement matrices, thereby immobilizing {Tc}. The oxidation state of Se following.bioremediation of Se by bacteria has also been determined by XANES. The XANES measurements were performed at the Stanford Synchrotron Radiation Laboratory (SSRL) and the National Synchrotron Light Source (NSLS) at the respective K edges of {Tc} (21.0 keV) and Se (12.7 keV). Comparison of the XANES spectra of Tc in untreated cement to Tc in slag treated cement and to the chemical shifts of reference materials, shows that the oxidation state of {Tc} is the same in both cements. Thus, the addition of a reducing agent to the cement formulation does not significantly reduce the {Tc}O{sub 4} The common soil bacterium, Bacillus subtilis, is known to incorporate Se on or within the cell wall when exposed to a SE(IV) solution. The Se XANES spectra of B. subtilis, as well as bacillus isolated from selenium rich soil, show that the organisms reduce selenite to the red allotrope of elemental Se.

  9. Heavy metal distribution and chemical speciation in tailings and soils around a Pb-Zn mine in Spain.

    PubMed

    Rodríguez, L; Ruiz, E; Alonso-Azcárate, J; Rincón, J

    2009-02-01

    Soil pollution by lead, zinc, cadmium and copper was characterized in the mine tailings and surrounding soils (arable and pasture lands) of an old Spanish Pb-Zn mine. Sixty soil samples were analyzed, determining the total metal concentration by acid digestion and the chemical fractionation of Pb and Zn by the modified BCR sequential extraction method. Samples belonging to mine waste areas showed the highest values, with mean concentrations of 28,453.50 mg kg(-1) for Pb, 7000.44 mg kg(-1) for Zn, 20.57 mg kg(-1) for Cd and 308.48 mg kg(-1) for Cu. High concentrations of Pb, Zn and Cd were found in many of the samples taken from surrounding arable and pasture lands, indicating a certain extent of spreading of heavy metal pollution. Acidic drainage and wind transport of dust were proposed as the main effects causing the dispersion of pollution. Sequential extraction showed that most of the Pb was associated with non-residual fractions, mainly in reducible form, in all the collected samples. Zn appeared mainly associated with the acid-extractable form in mine tailing samples, while the residual form was the predominant one in samples belonging to surrounding areas. Comparison of our results with several criteria reported in the literature for risk assessment in soils polluted by heavy metals showed the need to treat the mine tailings dumped in the mine area.

  10. The darkening of zinc yellow: XANES speciation of chromium in artist;s paints after light and chemical exposures

    SciTech Connect

    Zanella, Luciana; Casadio, Francesca; Gray, Kimberly A.; Warta, Richard; Ma, Qing; Gaillard, Jean-François

    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 in 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.

  11. Measurement of organic and elemental carbon in downtown Rome and background area: physical behavior and chemical speciation.

    PubMed

    Avino, Pasquale; Manigrasso, Maurizio; Rosada, Alberto; Dodaro, Alessandro

    2015-02-01

    A significant portion of the particulate matter is the total carbonaceous fraction (or total carbon, TC), composed of two main fractions, elemental carbon (EC) and organic carbon (OC), which shows a large variety of organic compounds, e.g. aliphatic, aromatic compounds, alcohols, acids, etc. In this paper, TC, EC and OC concentrations determined in a downtown Rome urban area are discussed considering the influence of meteorological conditions on the temporal-spatial aerosol distribution. Similar measurements were performed at ENEA Casaccia, an area outside Rome, which is considered as the ome background. Since 2000, TC, EC and OC measurements have been performed by means of an Ambient Carbon Particulate Monitor equipped with a NDIR detector. The EC and OC concentrations trends are compared with benzene and CO trends, which are specific indicators of autovehicular traffic, for identifying the primary EC and OC contributions and the secondary OC fraction origin. Further, a chemical investigation is reported for investigating how the main organic (i.e., n-alkanes, n-alkanoic acids, polyaromatic hydrocarbons and nitro-polyaromatic hydrocarbons) and inorganic (i.e., metals, ions) fractions vary their levels during the investigated period in relationship to new regulations and/or technological innovations.

  12. 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...

  13. Infrared hyperspectral tunable filter imaging spectrometer for remote leak detection, chemical speciation, and stack/vent analysis applications

    NASA Astrophysics Data System (ADS)

    Hinnrichs, Michele

    2002-02-01

    With support from the Department of Energy, the State of California and the Gas Technology Institute, Pacific Advanced Technology is developing a small field portable infrared imaging spectrometer (Sherlock) based on the advances in hyperspectral tunable filter technology, that will be applied to the detection of fugitive gas leaks. This imaging spectrometer uses the Image Multi-spectral Sensing (IMSS) diffractive optic tunable filter invented by Pacific Advanced Technology . The Sherlock has an embedded digital signal processor for real time detection of the gas leak while surrounded by severe background noise. The infrared sensor engine is a 256 x 320 midwave cooled focal plane array which spans the spectral range from 3 to 5 microns, ideal for most hydrocarbon leaks. The technology is by no means limited to this spectral region, and can just as easily work in the longwave infrared from 8 to 12 microns for chemical detection applications. This paper will present the design of the Sherlock camera as well as processed data collected at a gas processing plant and an instrumented kiln at LSU using the prototype camera. The processed data shows that the IMSS imaging spectrometer, using an all passive approach, has the sensitivity to detect methane gas leaks at short range with a flow rate as low as 0.01 scfm2. In addition, the IMSS imaging spectrometer can measure hot gas plumes at longer ranges. As will be shown in this paper the IMSS can detect and image warm species gas additives of methane and propane in the Kiln exhaust stack. The methane injected gas with a concentration of 72 ppm and the propane with a concentration of 49 ppm (as seen by the IMSS sensor) at a range of 60 meters. The atmospheric path was a stressing environment, being hot and humid, for any imaging infrared spectrometer.

  14. 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 ...

  15. On-line speciation of inorganic and methyl mercury in waters and fish tissues using polyaniline micro-column and flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS).

    PubMed

    Krishna, M V Balarama; Chandrasekaran, K; Karunasagar, D

    2010-04-15

    A simple and efficient method for the determination of ultra-trace amounts of inorganic mercury (iHg) and methylmercury (MeHg) in waters and fish tissues was developed using a micro-column filled with polyaniline (PANI) coupled online to flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS) system. Preliminary studies indicated that inorganic and methyl mercury species could be separated on PANI column in two different speciation approaches. At pH <3, only iHg could be sorbed and almost no adsorption of MeHg was found (speciation procedure 1). If the sample solution pH is approximately 7, both MeHg and iHg species could be sorbed on the PANI column. Subsequently both the Hg species were selectively eluted with 2% HCl and a mixture of 2% HCl and 0.02% thiourea respectively (speciation procedure 2). The adsorption percentage of iHg on the PANI column was unchanged even with acidity of the sample solution increased to 6 mol L(-1). Therefore, an acidic solution (5 mol L(-1) HCl), used for ultra-sound assisted extraction of the mercury species from biological samples, was used directly to separate MeHg from iHg in the fish tissues (tuna fish ERM-CE 463, ERM-CE 464 and IAEA-350) by PANI column using speciation procedure 1. The determined values were in good agreement with certified values. Under optimal conditions, the limits of detection (LODs) were 2.52 pg and 3.24 pg for iHg and MeHg (as Hg) respectively. The developed method was applied successfully to the direct determination of iHg and MeHg in various waters (tap water, lake water, ground water and sea-water) and the recoveries for the spiked samples were in the range of 96-102% for both the Hg species. PMID:20188947

  16. On-line speciation of inorganic and methyl mercury in waters and fish tissues using polyaniline micro-column and flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS).

    PubMed

    Krishna, M V Balarama; Chandrasekaran, K; Karunasagar, D

    2010-04-15

    A simple and efficient method for the determination of ultra-trace amounts of inorganic mercury (iHg) and methylmercury (MeHg) in waters and fish tissues was developed using a micro-column filled with polyaniline (PANI) coupled online to flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS) system. Preliminary studies indicated that inorganic and methyl mercury species could be separated on PANI column in two different speciation approaches. At pH <3, only iHg could be sorbed and almost no adsorption of MeHg was found (speciation procedure 1). If the sample solution pH is approximately 7, both MeHg and iHg species could be sorbed on the PANI column. Subsequently both the Hg species were selectively eluted with 2% HCl and a mixture of 2% HCl and 0.02% thiourea respectively (speciation procedure 2). The adsorption percentage of iHg on the PANI column was unchanged even with acidity of the sample solution increased to 6 mol L(-1). Therefore, an acidic solution (5 mol L(-1) HCl), used for ultra-sound assisted extraction of the mercury species from biological samples, was used directly to separate MeHg from iHg in the fish tissues (tuna fish ERM-CE 463, ERM-CE 464 and IAEA-350) by PANI column using speciation procedure 1. The determined values were in good agreement with certified values. Under optimal conditions, the limits of detection (LODs) were 2.52 pg and 3.24 pg for iHg and MeHg (as Hg) respectively. The developed method was applied successfully to the direct determination of iHg and MeHg in various waters (tap water, lake water, ground water and sea-water) and the recoveries for the spiked samples were in the range of 96-102% for both the Hg species.

  17. Experimental Determination of the Speciation, Partitioning, and Release of Perrhenate as a Chemical Surrogate for Pertechnetate from a Sodalite-Bearing Multiphase Ceramic Waste Form

    SciTech Connect

    Pierce, Eric M; Lukens, Wayne W; Fitts, Jeffrey P; Tang, Guoping; Jantzen, C M

    2013-01-01

    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 FBSR 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

  18. Experimental determination of the speciation, partitioning, and release of perrhenate as a chemical surrogate for pertechnetate from a sodalite-bearing multiphase ceramic waste form

    SciTech Connect

    Pierce, Eric M.; Lukens, Wayne W.; Fitts, Jeff. P.; Jantzen, Carol. M.; Tang, G.

    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 FBSR 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

  19. Environmental speciation of actinides.

    PubMed

    Maher, Kate; Bargar, John R; Brown, Gordon E

    2013-04-01

    Although minor in abundance in Earth's crust (U, 2-4 ppm; Th, 10-15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters, and some of the common U-containing minerals. We also discuss the interaction of U, Np, Pu, and Am solution complexes with common Earth materials, including minerals, colloids, gels, natural organic matter (NOM), and microbial organisms, based on simplified model system studies. These surface interactions can inhibit (e.g., sorption to mineral surfaces, formation of insoluble biominerals) or enhance (e.g., colloid-facilitated transport) the dispersal of light actinides in the biosphere and in some cases (e.g., interaction with dissimilatory metal-reducing bacteria, NOM, or Mn- and Fe-containing minerals) can modify the oxidation states and, consequently, the behavior of redox-sensitive light actinides (U, Np, and Pu). Finally, we review the speciation of U and Pu, their chemical transformations, and cleanup histories at several U.S. Department of Energy field sites that have been used to mill U ores, produce fissile materials for reactors and weapons, and store

  20. Environmental speciation of actinides.

    PubMed

    Maher, Kate; Bargar, John R; Brown, Gordon E

    2013-04-01

    Although minor in abundance in Earth's crust (U, 2-4 ppm; Th, 10-15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters, and some of the common U-containing minerals. We also discuss the interaction of U, Np, Pu, and Am solution complexes with common Earth materials, including minerals, colloids, gels, natural organic matter (NOM), and microbial organisms, based on simplified model system studies. These surface interactions can inhibit (e.g., sorption to mineral surfaces, formation of insoluble biominerals) or enhance (e.g., colloid-facilitated transport) the dispersal of light actinides in the biosphere and in some cases (e.g., interaction with dissimilatory metal-reducing bacteria, NOM, or Mn- and Fe-containing minerals) can modify the oxidation states and, consequently, the behavior of redox-sensitive light actinides (U, Np, and Pu). Finally, we review the speciation of U and Pu, their chemical transformations, and cleanup histories at several U.S. Department of Energy field sites that have been used to mill U ores, produce fissile materials for reactors and weapons, and store

  1. Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSm) and a multi-wavelength Aethalometer

    NASA Astrophysics Data System (ADS)

    Petit, J.-E.; Favez, O.; Sciare, J.; Crenn, V.; Sarda-Estève, R.; Bonnaire, N.; Močnik, G.; Dupont, J.-C.; Haeffelin, M.; Leoz-Garziandia, E.

    2014-09-01

    Aerosol Mass Spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaign. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artefact-free chemical information but for low-cost, and to perform robust monitoring over long-term period. When deployed in parallel with real-time Black Carbon (BC) measurements, the combined dataset allows for a quasi-comprehensive description of the whole PM1 fraction in near real-time. Here we present a 2 year long ACSM and BC datasets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite being representative of background PM levels of the region of Paris. This large dataset shows intense and time limited (few hours) pollution events observed during wintertime in the region of Paris pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2 year dataset for the major PM1 constituents (organic matter, nitrate, sulphate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions which information are mandatory for efficient mitigation strategies. While ammonium sulphate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but less expected, it also exhibits a significant contribution of regional and local emissions. Contribution of regional background OA is significant in spring and summer while a more pronounced local origin is evidenced during wintertime which pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main parameters controlling their temporal

  2. Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSM) and a multi-wavelength Aethalometer

    NASA Astrophysics Data System (ADS)

    Petit, J.-E.; Favez, O.; Sciare, J.; Crenn, V.; Sarda-Estève, R.; Bonnaire, N.; Močnik, G.; Dupont, J.-C.; Haeffelin, M.; Leoz-Garziandia, E.

    2015-03-01

    Aerosol mass spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaigns. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artifact-free chemical information but for low cost, and to perform robust monitoring over long-term periods. When deployed in parallel with real-time black carbon (BC) measurements, the combined data set allows for a quasi-comprehensive description of the whole PM1 fraction in near real time. Here we present 2-year long ACSM and BC data sets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite that is representative of background PM levels of the region of Paris. This large data set shows intense and time-limited (a few hours) pollution events observed during wintertime in the region of Paris, pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2-year data set for the major PM1 constituents (organic matter, nitrate, sulfate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions whose information is mandatory for efficient mitigation strategies. While ammonium sulfate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but, less expectedly, it also exhibits a significant contribution of regional and local emissions. The contribution of regional background organic aerosols (OA) is significant in spring and summer, while a more pronounced local origin is evidenced during wintertime, whose pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main

  3. A new view on gold speciation in sulfur-bearing hydrothermal fluids from in situ X-ray absorption spectroscopy and quantum-chemical modeling

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Tagirov, Boris R.; Schott, Jacques; Hazemann, Jean-Louis; Proux, Olivier

    2009-09-01

    Despite the common belief that Au I complexes with hydrogen sulfide ligands (H 2S/HS -) are the major carriers of gold in natural hydrothermal fluids, their identity, structure and stability are still subjects of debate. Here we present the first in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of the stability and structure of aqueous Au I-S complexes at temperatures and pressures ( T-P) typical of natural sulfur-rich ore-forming fluids. The solubility of native gold and the local atomic structure around the dissolved metal in S-NaOH-Na 2SO 4-H 2SO 4 aqueous solutions were characterized at temperatures 200-450 °C and pressures 300-600 bar using an X-ray cell that allows simultaneous measurement of the absolute concentration of the absorbing atom (Au) and its local atomic environment in the fluid phase. Structural and solubility data obtained from XAFS spectra, combined with quantum-chemical calculations of species geometries, show that gold bis(hydrogensulfide) Au(HS) 2- is the dominant Au species in neutral-to-basic solutions (5.5 ⩽ pH ⩽ 8.5; H 2O-S-NaOH) over a wide range of sulfur concentrations (0.2 < ΣS < 3.6 mol/kg), in agreement with previous solubility studies. Our results provide the first direct determination of this species structure, in which two sulfur atoms are in a linear geometry around Au I at an average distance of 2.29 ± 0.01 Å. At acidic conditions (1.5 ⩽ pH ⩽ 5.0; H 2O-S-Na 2SO 4-H 2SO 4), the Au atomic environment determined by XAFS is similar to that in neutral solutions. These findings, together with measured high Au solubilities, are inconsistent with the predominance of the gold hydrogensulfide Au(HS) 0 complex suggested by recent solubility studies. Our spectroscopic data and quantum-chemical calculations imply the formation of species composed of linear S-Au-S moieties, like the neutral [H 2S-Au-SH] complex. This species may account for the elevated Au solubilities in acidic fluids and vapors

  4. The Development and Uses of EPA's SPECIATE Database

    EPA Science Inventory

    SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic compounds (VOC) and particulate matter (PM) speciation profiles of air pollution sources. These source profiles can be used to (l) provide input to chemical mass balance (CMB) receptor mod...

  5. Hybridization and speciation.

    PubMed

    Abbott, R; Albach, D; Ansell, S; Arntzen, J W; Baird, S J E; Bierne, N; Boughman, J; Brelsford, A; Buerkle, C A; Buggs, R; Butlin, R K; Dieckmann, U; Eroukhmanoff, F; Grill, A; Cahan, S H; Hermansen, J S; Hewitt, G; Hudson, A G; Jiggins, C; Jones, J; Keller, B; Marczewski, T; Mallet, J; Martinez-Rodriguez, P; Möst, M; Mullen, S; Nichols, R; Nolte, A W; Parisod, C; Pfennig, K; Rice, A M; Ritchie, M G; Seifert, B; Smadja, C M; Stelkens, R; Szymura, J M; Väinölä, R; Wolf, J B W; Zinner, D

    2013-02-01

    Hybridization has many and varied impacts on the process of speciation. Hybridization may slow or reverse differentiation by allowing gene flow and recombination. It may accelerate speciation via adaptive introgression or cause near-instantaneous speciation by allopolyploidization. It may have multiple effects at different stages and in different spatial contexts within a single speciation event. We offer a perspective on the context and evolutionary significance of hybridization during speciation, highlighting issues of current interest and debate. In secondary contact zones, it is uncertain if barriers to gene flow will be strengthened or broken down due to recombination and gene flow. Theory and empirical evidence suggest the latter is more likely, except within and around strongly selected genomic regions. Hybridization may contribute to speciation through the formation of new hybrid taxa, whereas introgression of a few loci may promote adaptive divergence and so facilitate speciation. Gene regulatory networks, epigenetic effects and the evolution of selfish genetic material in the genome suggest that the Dobzhansky-Muller model of hybrid incompatibilities requires a broader interpretation. Finally, although the incidence of reinforcement remains uncertain, this and other interactions in areas of sympatry may have knock-on effects on speciation both within and outside regions of hybridization.

  6. Arsenic Speciation of Terrestrial Invertebrates

    SciTech Connect

    Moriarty, M.M.; Koch, I.; Gordon, R.A.; Reimer, K.J. ); )

    2009-07-01

    The distribution and chemical form (speciation) of arsenic in terrestrial food chains determines both the amount of arsenic available to higher organisms, and the toxicity of this metalloid in affected ecosystems. Invertebrates are part of complex terrestrial food webs. This paper provides arsenic concentrations and arsenic speciation profiles for eight orders of terrestrial invertebrates collected at three historical gold mine sites and one background site in Nova Scotia, Canada. Total arsenic concentrations, determined by inductively coupled plasma mass spectrometry (ICP-MS), were dependent upon the classification of invertebrate. Arsenic species were determined by high-performance liquid chromatography (HPLC) ICP-MS and X-ray absorption spectroscopy (XAS). Invertebrates were found by HPLC ICP-MS to contain predominantly arsenite and arsenate in methanol/water extracts, while XAS revealed that most arsenic is bound to sulfur in vivo. Examination of the spatial distribution of arsenic within an ant tissue highlighted the differences between exogenous and endogenous arsenic, as well as the extent to which arsenic is transformed upon ingestion. Similar arsenic speciation patterns for invertebrate groups were observed across sites. Trace amounts of arsenobetaine and arsenocholine were identified in slugs, ants, and spiders.

  7. 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...

  8. ELEMENTAL SPECIATION IN ENVIRONMENTAL EXPOSURE ASSESSMENT MATRICES

    EPA Science Inventory

    Arsenic and tin are two trace metals where exposure assessments have moved towards a speciation based approach because the toxicity is very chemical form dependent. This toxicity difference can be one of many factors which influence the formulation of certain regulations. For a...

  9. Chemical speciation of strontium, americium, and curium in high level waste: Predictive modeling of phase partitioning during tank processing. Annual progress report, October 1996--September 1997

    SciTech Connect

    Felmy, A.R.; Choppin, G.

    1997-12-31

    'The program at Florida State University was funded to collaborate with Dr. A. Felmy (PNNL) on speciation in high level wastes and with Dr. D. Rai (PNNL) on redox of Pu under high level waste conditions. The funding provided support for 3 research associates (postdoctoral researchers) under Professor G. R. Choppin as P.I. Dr. Kath Morris from U. Manchester (Great Britain), Dr. Dean Peterman and Dr. Amy Irwin (both from U. Cincinnati) joined the laboratory in the latter part of 1996. After an initial training period to become familiar with basic actinide chemistry and radiochemical techniques, they began their research. Dr. Peterman was assigned the task of measuring Th-EDTA complexation prior to measuring Pu(IV)-EDTA complexation. These studies are associated with the speciation program with Dr. Felmy. Drs. Morris and Irwin initiated research on redox of plutonium with agents present in the Hanford Tanks as a result of radiolysis or from use in separations. The preliminary results obtained thus far are described in this report. It is expected that the rate of progress will continue to increase significantly as the researchers gain more experience with plutonium chemistry.'

  10. 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. PMID:26846236

  11. 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...

  12. Major 20th century changes of the content and chemical speciation of organic carbon archived in Alpine ice cores: Implications for the long-term change of organic aerosol over Europe

    NASA Astrophysics Data System (ADS)

    Legrand, M.; Preunkert, S.; May, B.; Guilhermet, J.; Hoffman, H.; Wagenbach, D.

    2013-05-01

    Dissolved organic carbon (DOC) and an extended array of organic compounds were investigated in an Alpine ice core covering the 1920-1988 time period. Based on this, a reconstruction was made of the long-term trends of water-soluble organic carbon (WSOC) aerosol in the European atmosphere. It is shown that light mono- and dicarboxylates, humic-like substances, and formaldehyde account together for more than half of the DOC content of ice. This extended chemical speciation of DOC is used to estimate the DOC fraction present in ice that is related to WSOC aerosol and its change over the past. It is suggested that after World War II, the WSOC levels have been enhanced by a factor of 2 and 3 in winter and summer, respectively. In summer, the fossil fuel contribution to the enhancement is estimated to be rather small, suggesting that it arises mainly from an increase in biogenic sources of WSOC.

  13. Theory and speciation.

    PubMed

    Turelli, M; Barton, N H.; Coyne, J A.

    2001-07-01

    The study of speciation has become one of the most active areas of evolutionary biology, and substantial progress has been made in documenting and understanding phenomena ranging from sympatric speciation and reinforcement to the evolutionary genetics of postzygotic isolation. This progress has been driven largely by empirical results, and most useful theoretical work has concentrated on making sense of empirical patterns. Given the complexity of speciation, mathematical theory is subordinate to verbal theory and generalizations about data. Nevertheless, mathematical theory can provide a useful classification of verbal theories; can help determine the biological plausibility of verbal theories; can determine whether alternative mechanisms of speciation are consistent with empirical patterns; and can occasionally provide predictions that go beyond empirical generalizations. We discuss recent examples of progress in each of these areas.

  14. Assessment of contamination, distribution and chemical speciation of trace metals in water column in the Dakar coast and the Saint Louis estuary from Senegal, West Africa.

    PubMed

    Diop, Cheikh; Dewaelé, Dorothée; Diop, Mamadou; Touré, Aminata; Cabral, Mathilde; Cazier, Fabrice; Fall, Mamadou; Diouf, Amadou; Ouddane, Baghdad

    2014-09-15

    The water column from Dakar coast and Saint Louis estuary in Senegal, West Africa, was sampled in order to measure the contamination level by trace metals. The speciation of metals in water allowed performing a distribution between dissolved and particulate trace metals. For the dissolved metals, the metallic concentration and repartition between the organic fraction and the inorganic fraction were performed. The results show that the pollution of the estuary was more serious than in Dakar coast for Co, Cr, Ni, Pb and Zn; while, Cd and Cu were higher in Dakar coast. A strong affinity between metals and suspended particles has been revealed. Dissolved metals that have a tendency to form organic metal complexes are in decreasing order: Cd, Zn, Pb, Co=Cr=Mn, Cu and Ni. The results showed that the mobility of trace metals in estuary is controlled by dissolved organic carbon, while in coast it depends on chlorides.

  15. What Is Speciation?

    PubMed

    Shapiro, B Jesse; Leducq, Jean-Baptiste; Mallet, James

    2016-03-01

    Concepts and definitions of species have been debated by generations of biologists and remain controversial. Microbes pose a particular challenge because of their genetic diversity, asexual reproduction, and often promiscuous horizontal gene transfer (HGT). However, microbes also present an opportunity to study and understand speciation because of their rapid evolution, both in nature and in the lab, and small, easily sequenced genomes. Here, we review how microbial population genomics has enabled us to catch speciation "in the act" and how the results have challenged and enriched our concepts of species, with implications for all domains of life. We describe how recombination (including HGT and introgression) has shaped the genomes of nascent microbial, animal, and plant species and argue for a prominent role of natural selection in initiating and maintaining speciation. We ask how universal is the process of speciation across the tree of life, and what lessons can be drawn from microbes? Comparative genomics showing the extent of HGT in natural populations certainly jeopardizes the relevance of vertical descent (i.e., the species tree) in speciation. Nevertheless, we conclude that species do indeed exist as clusters of genetic and ecological similarity and that speciation is driven primarily by natural selection, regardless of the balance between horizontal and vertical descent. PMID:27030977

  16. What Is Speciation?

    PubMed Central

    Shapiro, B. Jesse; Leducq, Jean-Baptiste; Mallet, James

    2016-01-01

    Concepts and definitions of species have been debated by generations of biologists and remain controversial. Microbes pose a particular challenge because of their genetic diversity, asexual reproduction, and often promiscuous horizontal gene transfer (HGT). However, microbes also present an opportunity to study and understand speciation because of their rapid evolution, both in nature and in the lab, and small, easily sequenced genomes. Here, we review how microbial population genomics has enabled us to catch speciation “in the act” and how the results have challenged and enriched our concepts of species, with implications for all domains of life. We describe how recombination (including HGT and introgression) has shaped the genomes of nascent microbial, animal, and plant species and argue for a prominent role of natural selection in initiating and maintaining speciation. We ask how universal is the process of speciation across the tree of life, and what lessons can be drawn from microbes? Comparative genomics showing the extent of HGT in natural populations certainly jeopardizes the relevance of vertical descent (i.e., the species tree) in speciation. Nevertheless, we conclude that species do indeed exist as clusters of genetic and ecological similarity and that speciation is driven primarily by natural selection, regardless of the balance between horizontal and vertical descent. PMID:27030977

  17. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

    PubMed

    Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

    2015-01-01

    Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide

  18. Characterizing phosphorus speciation of Chesapeake Bay sediments using chemical extraction, 31P NMR, and X-ray absorption fine structure spectroscopy.

    PubMed

    Li, Wei; Joshi, Sunendra R; Hou, Guangjin; Burdige, David J; Sparks, Donald L; Jaisi, Deb P

    2015-01-01

    Nutrient contamination has been one of the lingering issues in the Chesapeake Bay because the bay restoration is complicated by temporally and seasonally variable nutrient sources and complex interaction between imported and regenerated nutrients. Differential reactivity of sedimentary phosphorus (P) pools in response to imposed biogeochemical conditions can record past sediment history and therefore a detailed sediment P speciation may provide information on P cycling particularly the stability of a P pool and the formation of one pool at the expense of another. This study examined sediment P speciation from three sites in the Chesapeake Bay: (i) a North site in the upstream bay, (ii) a middle site in the central bay dominated by seasonally hypoxic bottom water, and (iii) a South site at the bay-ocean boundary using a combination of sequential P extraction (SEDEX) and spectroscopic techniques, including (31)P NMR, P X-ray absorption near edge structure spectroscopy (XANES), and Fe extended X-ray absorption fine structure (EXAFS). Results from sequential P extraction reveal that sediment P is composed predominantly of ferric Fe-bound P and authigenic P, which was further confirmed by solid-state (31)P NMR, XANES, and EXAFS analyses. Additionally, solution (31)P NMR results show that the sediments from the middle site contain high amounts of organic P such as monoesters and diesters, compared to the other two sites, but that these compounds rapidly decrease with sediment depth indicating remineralized P could have precipitated as authigenic P. Fe EXAFS enabled to identify the changes in Fe mineral composition and P sinks in response to imposed redox condition in the middle site sediments. The presence of lepidocrocite, vermiculite, and Fe smectite in the middle site sediments indicates that some ferric Fe minerals can still be present along with pyrite and vivianite, and that ferric Fe-bound P pool can be a major P sink in anoxic sediments. These results provide

  19. ACTRIS ACSM intercomparison - Part 1: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with co-located instruments

    NASA Astrophysics Data System (ADS)

    Crenn, V.; Sciare, J.; Croteau, P. L.; Verlhac, S.; Fröhlich, R.; Belis, C. A.; Aas, W.; Äijälä, M.; Alastuey, A.; Artiñano, B.; Baisnée, D.; Bonnaire, N.; Bressi, M.; Canagaratna, M.; Canonaco, F.; Carbone, C.; Cavalli, F.; Coz, E.; Cubison, M. J.; Esser-Gietl, J. K.; Green, D. C.; Gros, V.; Heikkinen, L.; Herrmann, H.; Lunder, C.; Minguillón, M. C.; Močnik, G.; O'Dowd, C. D.; Ovadnevaite, J.; Petit, J.-E.; Petralia, E.; Poulain, L.; Priestman, M.; Riffault, V.; Ripoll, A.; Sarda-Estève, R.; Slowik, J. G.; Setyan, A.; Wiedensohler, A.; Baltensperger, U.; Prévôt, A. S. H.; Jayne, J. T.; Favez, O.

    2015-12-01

    As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall - early-winter period (November-December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some

  20. Speciation of Cr(III) and Cr(VI) in environmental samples determined by selective separation and preconcentration on silica gel chemically modified with niobium(V) oxide.

    PubMed

    Martendal, Edmar; Maltez, Heloisa França; Carasek, Eduardo

    2009-01-15

    In this study a new method for chromium speciation in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The adsorption behavior of Cr(III) and Cr(VI) on Nb2O5-SiO2 allowed the selective separation of Cr(III) from Cr(VI) in the pH range of 6-9. Thus, a method for Cr(III) preconcentration and extraction using Nb2O5-SiO2 was developed. Total chromium was determined after the reduction of Cr(VI) to Cr(III) using sodium sulfite in acidic medium. The operational variables of the preconcentration and reduction procedures were optimized through full factorial and Doehlert designs. The limit of detection for Cr(III) was 0.34microgL(-1) and the precision was below 4.6%. Results for recovery tests using different environmental samples were between 90 and 105%. Certified reference materials (NIST 1640 and NIST 1643e) were analyzed in order to check the accuracy of the proposed method, and the results were in agreement with the certified values.

  1. Speciation of Cr(III) and Cr(VI) in environmental samples determined by selective separation and preconcentration on silica gel chemically modified with niobium(V) oxide.

    PubMed

    Martendal, Edmar; Maltez, Heloisa França; Carasek, Eduardo

    2009-01-15

    In this study a new method for chromium speciation in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The adsorption behavior of Cr(III) and Cr(VI) on Nb2O5-SiO2 allowed the selective separation of Cr(III) from Cr(VI) in the pH range of 6-9. Thus, a method for Cr(III) preconcentration and extraction using Nb2O5-SiO2 was developed. Total chromium was determined after the reduction of Cr(VI) to Cr(III) using sodium sulfite in acidic medium. The operational variables of the preconcentration and reduction procedures were optimized through full factorial and Doehlert designs. The limit of detection for Cr(III) was 0.34microgL(-1) and the precision was below 4.6%. Results for recovery tests using different environmental samples were between 90 and 105%. Certified reference materials (NIST 1640 and NIST 1643e) were analyzed in order to check the accuracy of the proposed method, and the results were in agreement with the certified values. PMID:18455867

  2. Speciation and bifurcations.

    PubMed

    Volkenstein, M V; Livshits, M A

    1989-01-01

    The interrelations of physics and biology are discussed. It is shown that Darwin can be considered as one of the founders of the important field of contemporary physics called physics of dissipative structures or synergetics. The theories of gradual and punctual evolution are presented. The contradiction between these theories can be solved on the basis of molecular theory of evolution and on the basis of the phenomenological physical treatment. The general physical properties of living systems, considered as open systems being far from equilibrium, are listed and simple non-linear mathematical models describing gradual and punctual speciation are suggested. The usual pictures which present these two kinds of speciation can possess physico-mathematical sense. Punctuated speciation means bifurcation, a kind of non-equilibrium phase transition.

  3. Sexual selection and speciation.

    PubMed

    Panhuis, T M.; Butlin, R; Zuk, M; Tregenza, T

    2001-07-01

    The power of sexual selection to drive changes in mate recognition traits gives it the potential to be a potent force in speciation. Much of the evidence to support this possibility comes from comparative studies that examine differences in the number of species between clades that apparently differ in the intensity of sexual selection. We argue that more detailed studies are needed, examining extinction rates and other sources of variation in species richness. Typically, investigations of extant natural populations have been too indirect to convincingly conclude speciation by sexual selection. Recent empirical work, however, is beginning to take a more direct approach and rule out confounding variables.

  4. Phylogenetics and speciation.

    PubMed

    Barraclough, T G.; Nee, S

    2001-07-01

    Species-level phylogenies derived from molecular data provide an indirect record of the speciation events that have led to extant species. This offers enormous potential for investigating the general causes and rates of speciation within clades. To make the most of this potential, we should ideally sample all the species in a higher group, such as a genus, ensure that those species reflect evolutionary entities within the group, and rule out the effects of other processes, such as extinction, as explanations for observed patterns. We discuss recent practical and theoretical advances in this area and outline how future work should benefit from incorporating data from genealogical and phylogeographical scales.

  5. 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

  6. ORGANIC SPECIATION SAMPLING ARTIFACTS

    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 ...

  7. Population differentiation without speciation

    PubMed Central

    Magurran, A. E.

    1998-01-01

    Population differentiation is often viewed as an important step towards speciation, and part of the rationale for conserving variation at the intraspecific level is that the potential to generate more biological diversity should be retained. Yet, speciation is not an inevitable consequence of population divergence. This paper reviews recent work on the Trinidadian guppy, Poecilia reticulata, a species that is renowned for its capacity for population differentiation. Guppy populations evolve rapidly, within 101 to 102 generations, as a response to changes in selection exerted by predators. The rates of evolution involved can be up to seven orders of magnitude greater than those seen in the fossil record. Sexual selection, particuarly female choice, appears to reinforce the divergence that natural selection has generated. Perplexingly, however, there is no reproductive isolation (either prezygotic or postzygotic) between populations, even those that have been separated for at least 106 generations. Sexual conflict may be the key to explaining this absence of speciation. Male reproductive behaviour, particularly the high incidence of sneaky mating, may be instrumental in producing sufficient gene flow to prevent reproductive isolation. Sneaky mating has the potential to undermine female choice, and is known to be an important means of sperm transfer in wild populations. Sexual dimorphism, also a result of sexual conflict in guppies, may inhibit speciation in another way. Morphological differences between the sexes, that have arisen for reproductive reasons, mean that males and females are pre-adapted for different foraging niches. This, in turn, reduces the opportunity for the development of feeding polymorphisms, a mechanism that seems to have been important in the sympatric speciation of other fish species.

  8. 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.

  9. The evolutionary genetics of speciation.

    PubMed Central

    Coyne, J A; Orr, H A

    1998-01-01

    The last decade has brought renewed interest in the genetics of speciation, yielding a number of new models and empirical results. Defining speciation as 'the origin of reproductive isolation between two taxa', we review recent theoretical studies and relevant data, emphasizing the regular patterns seen among genetic analyses. Finally, we point out some important and tractable questions about speciation that have been neglected. PMID:9533126

  10. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments.

  11. 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. ...

  12. XAS Studies of Se Speciation in Selenite-Fed Rats

    PubMed Central

    Weekley, Claire M.; Aitken, Jade B.; Witting, Paul K.; Harris, Hugh H.

    2014-01-01

    The biological activity of selenium is dependent on its chemical form. Therefore, knowledge of Se chemistry in vivo is required for efficacious use of selenium compounds in disease prevention and treatment. Using X-ray absorption spectroscopy, Se speciation in the kidney, liver, heart, spleen, testis and red blood cells of rats fed control (~0.3 ppm Se) or selenite-supplemented (1 ppm or 5 ppm Se) diets for 3 or 6 weeks, was investigated. X-ray absorption spectroscopy revealed the presence of Se–Se and Se–C species in the kidney and liver, and Se–S species in the kidney, but not the liver. X-ray absorption near edge structure (XANES) spectra showed that there was variation in speciation in the liver and kidneys, but Se speciation was much more uniform in the remaining organs. Using principal component analysis (PCA) to interpret the Se K-edge X-ray absorption spectra, we were able to directly compare the speciation of Se in two different models of selenite metabolism – human lung cancer cells and rat tissues. The effects of Se dose, tissue type and duration of diet on selenium speciation in rat tissues were investigated, and a relationship between the duration of the diet (3 weeks versus 6 weeks) and selenium speciation was observed. PMID:25363824

  13. Chemical speciation of PM emissions from heavy-duty diesel vehicles equipped with diesel particulate filter (DPF) and selective catalytic reduction (SCR) retrofits

    NASA Astrophysics Data System (ADS)

    Biswas, Subhasis; Verma, Vishal; Schauer, James J.; Sioutas, Constantinos

    Four heavy-duty diesel vehicles (HDDVs) in six retrofitted configurations (CRT ®, V-SCRT ®, Z-SCRT ®, Horizon, DPX and CCRT ®) and a baseline vehicle operating without after--treatment were tested under cruise (50 mph), transient UDDS and idle driving modes. As a continuation of the work by Biswas et al. [Biswas, S., Hu, S., Verma, V., Herner, J., Robertson, W.J., Ayala, A., Sioutas, C., 2008. Physical properties of particulate matter (PM) from late model heavy-duty diesel vehicles operating with advanced emission control technologies. Atmospheric Environment 42, 5622-5634.] on particle physical parameters, this paper focuses on PM chemical characteristics (Total carbon [TC], Elemental carbon [EC], Organic Carbon [OC], ions and water-soluble organic carbon [WSOC]) for cruise and UDDS cycles only. Size-resolved PM collected by MOUDI-Nano-MOUDI was analyzed for TC, EC and OC and ions (such as sulfate, nitrate, ammonium, potassium, sodium and phosphate), while Teflon coated glass fiber filters from a high volume sampler were extracted to determine WSOC. The introduction of retrofits reduced PM mass emissions over 90% in cruise and 95% in UDDS. Similarly, significant reductions in the emission of major chemical constituents (TC, OC and EC) were achieved. Sulfate dominated PM composition in vehicle configurations (V-SCRT ®-UDDS, Z-SCRT ®-Cruise, CRT ® and DPX) with considerable nucleation mode and TC was predominant for configurations with less (Z-SCRT ®-UDDS) or insignificant (CCRT ®, Horizon) nucleation. The transient operation increases EC emissions, consistent with its higher accumulation PM mode content. In general, solubility of organic carbon is higher (average ˜5 times) for retrofitted vehicles than the baseline vehicle. The retrofitted vehicles with catalyzed filters (DPX, CCRT ®) had decreased OC solubility (WSOC/OC: 8-25%) unlike those with uncatalyzed filters (SCRT ®s, Horizon; WSOC/OC ˜ 60-100%). Ammonium was present predominantly in the

  14. Semi-continuous sampling of health relevant atmospheric particle subfractions for chemical speciation using a rotating drum impactor in series with sequential filter sampler.

    PubMed

    Li, Fengxia; Schnelle-Kreis, Jürgen; Karg, Erwin; Cyrys, Josef; Gu, Jianwei; Orasche, Jürgen; Abbaszade, Gülcin; Peters, Annette; Zimmermann, Ralf

    2016-04-01

    To achieve unattended continuous long-term (eg., 1 week) sampling of size-segregated 24-h ambient particulate matter (PM), a sampling strategy of a modified 3-stage rotating drum impactor (RDI) in series with a sequential filter sampler was introduced and verified in a field campaign. Before the field sampling, lab experiment was conducted to test the collection efficiency of the third stage of the RDI using the quartz-fiber filter (QFF) as the substrate. The measured value is 0.36 μm, which is larger than the nominal value 0.1 μm. A fast direct analysis of organic species in all size fractions (<0.36, 0.36-1, 1-2.4, and 2.4-10 μm) of 24-h ambient samples was done using in situ derivatization thermal desorption gas chromatography time-of-flight mass spectrometry (IDTD-GC-TOFMS). A few secondary originated polar markers (dicarboxylic acids, cis-pinonic acid, etc.) were introduced and evaluated using this method for the first time and quantified simultaneously with polycyclic aromatic hydrocarbons (PAH) in the filter samples (<0.36 μm). For the other RDI strip samples (0.36-1, 1-2.4, and 2.4-10 μm), PAH and levoglucosan were quantified. The comparability of two such sampler sets was verified with respect to the PM collection profile of the two RDIs as well as measured concentration of chemical compounds in each sampled size fraction, so that a future epidemiological study on the relationship between the finest PM/its chemical composition and health outcome could be carried out through parallel sampling at two sites. The internal correlations between the size-segregated organic compounds are discussed. Besides, the correlations between the size-segregated organic species and size-segregated particulate number concentration (PNC) as well as meteorological parameter are discussed as well. PMID:26676546

  15. Speciation in granitic melts

    SciTech Connect

    Burnham, C.W.; Nekvasil, H.

    1985-01-01

    Refinement of the cryoscopic equations for the major granitic melt components, NaAlSi/sub 3/O/sub 8/(ab), CaAl/sub 2/O/sub 8/(an), KAlSi/sub 3/O/sub 8/(or), and Si/sub 4/O/sub 8/(qz), has led to the recognition of several major speciation reactions in anhydrous and hydrous melts of the system Ab-An-Or-Qz-H/sub 2/O. These reactions involve either dissociation of the feldspar-like components, as in incongruent melting, or interaction between them and qz. In all cases of interaction, one of the speciation products has the stoichiometry of dpy or py (pyrophyllite) (Al/sub 1.455/Si/sub 2.91/O/sub 8/ +/- 0.73H/sub 2/O), in which Al is presumed to be in either fivefold (dpy) or sixfold (py) coordination. The py component also is a major product of speciation by interaction between sil (Al/sub 3.2/Si/sub 1.6/O/sub 8/) and qz in peraluminous melts of the system Ab-Or-Qz-Sil-H/sub 2/O; as a consequence, the quartz liquidus field boundary is shifted to lower temperatures and toward qz. There is no evidence in peraluminous haplogranite melts for the existence of a muscovite-like species. Application of the refined thermodynamic model to the system Ab-Qz-Eu - H/sub 2/O at 2.0 kbar predicts the occurrence of a eu and qz-consuming reaction that produces a petalite-like species and a consequent dramatic shift in liquidus field boundaries. Higher pressures favor conversion of pe to qz + sp. In the spodumene-like species, sp, Al presumably is six-coordinated.

  16. The drivers of tropical speciation.

    PubMed

    Smith, Brian Tilston; McCormack, John E; Cuervo, Andrés M; Hickerson, Michael J; Aleixo, Alexandre; Cadena, Carlos Daniel; Pérez-Emán, Jorge; Burney, Curtis W; Xie, Xiaoou; Harvey, Michael G; Faircloth, Brant C; Glenn, Travis C; Derryberry, Elizabeth P; Prejean, Jesse; Fields, Samantha; Brumfield, Robb T

    2014-11-20

    Since the recognition that allopatric speciation can be induced by large-scale reconfigurations of the landscape that isolate formerly continuous populations, such as the separation of continents by plate tectonics, the uplift of mountains or the formation of large rivers, landscape change has been viewed as a primary driver of biological diversification. This process is referred to in biogeography as vicariance. In the most species-rich region of the world, the Neotropics, the sundering of populations associated with the Andean uplift is ascribed this principal role in speciation. An alternative model posits that rather than being directly linked to landscape change, allopatric speciation is initiated to a greater extent by dispersal events, with the principal drivers of speciation being organism-specific abilities to persist and disperse in the landscape. Landscape change is not a necessity for speciation in this model. Here we show that spatial and temporal patterns of genetic differentiation in Neotropical birds are highly discordant across lineages and are not reconcilable with a model linking speciation solely to landscape change. Instead, the strongest predictors of speciation are the amount of time a lineage has persisted in the landscape and the ability of birds to move through the landscape matrix. These results, augmented by the observation that most species-level diversity originated after episodes of major Andean uplift in the Neogene period, suggest that dispersal and differentiation on a matrix previously shaped by large-scale landscape events was a major driver of avian speciation in lowland Neotropical rainforests.

  17. The drivers of tropical speciation.

    PubMed

    Smith, Brian Tilston; McCormack, John E; Cuervo, Andrés M; Hickerson, Michael J; Aleixo, Alexandre; Cadena, Carlos Daniel; Pérez-Emán, Jorge; Burney, Curtis W; Xie, Xiaoou; Harvey, Michael G; Faircloth, Brant C; Glenn, Travis C; Derryberry, Elizabeth P; Prejean, Jesse; Fields, Samantha; Brumfield, Robb T

    2014-11-20

    Since the recognition that allopatric speciation can be induced by large-scale reconfigurations of the landscape that isolate formerly continuous populations, such as the separation of continents by plate tectonics, the uplift of mountains or the formation of large rivers, landscape change has been viewed as a primary driver of biological diversification. This process is referred to in biogeography as vicariance. In the most species-rich region of the world, the Neotropics, the sundering of populations associated with the Andean uplift is ascribed this principal role in speciation. An alternative model posits that rather than being directly linked to landscape change, allopatric speciation is initiated to a greater extent by dispersal events, with the principal drivers of speciation being organism-specific abilities to persist and disperse in the landscape. Landscape change is not a necessity for speciation in this model. Here we show that spatial and temporal patterns of genetic differentiation in Neotropical birds are highly discordant across lineages and are not reconcilable with a model linking speciation solely to landscape change. Instead, the strongest predictors of speciation are the amount of time a lineage has persisted in the landscape and the ability of birds to move through the landscape matrix. These results, augmented by the observation that most species-level diversity originated after episodes of major Andean uplift in the Neogene period, suggest that dispersal and differentiation on a matrix previously shaped by large-scale landscape events was a major driver of avian speciation in lowland Neotropical rainforests. PMID:25209666

  18. Speciation and phytoavailability of lead and antimony in a small arms range soil amended with mussel shell, cow bone and biochar: EXAFS spectroscopy and chemical extractions.

    PubMed

    Ahmad, Mahtab; Lee, Sang Soo; Lim, Jung Eun; Lee, Sung-Eun; Cho, Ju Sik; Moon, Deok Hyun; Hashimoto, Yohey; Ok, Yong Sik

    2014-01-01

    Mussel shell (MS), cow bone (CB) and biochar (BC) were selected to immobilize metals in an army firing range soil. Amendments were applied at 5% (wt) and their efficacies were determined after 175 d. For metal phytoavailability test, maize (Zea mays L.) plants were cultivated for 3weeks. Results showed that all amendments decreased the exchangeable Pb by up to 99% in planted/unplanted soils. Contrarily, exchangeable Sb were increased in the MS- and CB-amended soils. The rise in soil pH (~1 unit) by the amendments affected Pb and Sb mobility in soils. Bioavailability of Pb to maize was reduced by up to 71% in the amended soils. The Sb uptake to maize was decreased by up to 53.44% in the BC-amended soil. Sequential chemical extractions showed the transformation of easily available Pb to stable residual form with the amendment treatments. Scanning electron microscopic elemental dot mapping revealed the Pb association with Al and Si in the MS-amended soil and that with P in the CB- and BC-amended soils. Additionally, the extended X-ray absorption fine structure spectroscopic analysis indicated the transformation of organic bound Pb in unamended control soil to relatively more stable Pb-hydroxide (Ksp=10(-17.1)), chloropyromorphite (Ksp=10(-84.4)) and Pb-phosphate (Ksp=10(-23.8)) in soils amended with MS, CB and BC, respectively. Application of BC was the best in decreasing the phytoavailability of Pb and Sb in the studied army firing range soil.

  19. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

    PubMed

    Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

    2016-04-22

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a

  20. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis

    PubMed Central

    Larsen, K.K.; Wielandt, D.; Schiller, M.; Bizzarro, M.

    2016-01-01

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr3+, CrCl2+ and CrCl2+) with equilibrium mass-dependent isotope fractionation spanning a range of ~1‰/amu and consistent with theory. The heaviest isotopes partition into Cr3+, intermediates in CrCl2+ and the lightest in CrCl2+/CrCl3°. Thus, for a typical reported loss of ~25% Cr (in the form of Cr3+) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected 53Cr/52Cr (μ53 Cr* of 5.2 ppm) and 54Cr/52Cr (μ54Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr3+ by >5 days exposure to HNO3 —H2O2 solutions at room temperature, resulting in >~98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a chromatographic elution strategy that

  1. Chemical mass balance (CMB) source apportionment and organic speciation of PM(2.5) in Missoula, Montana including the 2000 wildfire season

    NASA Astrophysics Data System (ADS)

    Ward, Tony J.

    A yearlong sampling program for PM2.5, Semi- Volatile Organic Compounds (SVOCs), and Volatile Organic Compounds (VOCs) was conducted in 2000/2001. The data were used in a Chemical Mass Balance (CMB) Source Apportionment Model (Version 8.0) to apportion the sources of PM2.5 in the Missoula Valley. Results showed that wood combustion contributed an average of 41% to the fine fraction throughout the year. The second largest source of PM 2.5 was diesel (19%), followed by ammonium nitrate (17%), the kraft recovery boilers from Smurfit-Stone Container (14%), other hog fuel boilers (6%), and street sand (5%). Results also showed that PM2.5 levels and contributions from sources were consistent on both sides of the Missoula Valley, but VOCs were twice as high in Missoula compared to Frenchtown. Another aspect of this program was to investigate the organic fraction of the Missoula Valley PM2.5 by evaluating a modified Federal Reference Method (FRM) PM2.5 sampler. A method comparison was also made between sampling for SVOCs using the modified PM2.5 sampler and in using a Hi-volume Polyurethane Foam (PUF) sampler. Results showed that the PM 2.5 PUF measured more of the lighter SVOCs compared to the Hi-vol PUF sampler. This is most likely the result of the higher flows through the Hi-vol PUF which ``strip'' the lighter organics from the surface of the filter. The wildland fires of summer 2000 comprised one of the most severe fire seasons is U.S. history, and had a direct impact on the city of Missoula. Sampling in Missoula was already in progress when the fires began and smoke started rolling into the Missoula Valley. Samples were collected before, during, and after the 2000 fire season, and a detailed characterization of particulate and gaseous emissions from extensive wildland fires was obtained. The 2000/2001 CMB Sampling Program data collected during the 2000 fire season suggest that the main health impacts to downwind populations reside in the fine particulate exposures

  2. 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 ...

  3. A personal particle speciation sampler.

    PubMed

    Hering, Susanne; Kreisberg, Nathan; John, Walter

    2003-02-01

    Fuller understanding of personal exposures to particulate matter with aerodynamic diameters below 2.5 microm (PM2.5*) requires a personal sampler suitable for assaying not only PM2.5 mass but also its major chemical constituents: elemental carbon, organic carbon, sulfates, and nitrates. The goal to measure these constituents simultaneously imposes several constraints on personal sampler design. The aim of this project was to develop a sampler within these constraints that would be suitable for personal monitoring over 8 hours. In addition, with the intent to improve the precision of mass measurements, we investigated offline use of beta attenuation. The personal particle speciation sampler (PPSS) includes an inlet to remove particles larger than 2.5 microm, 2 sampling channels, and a pump with flow control. One channel serves for measuring particle mass and inorganic ions; the other, for measuring organic carbon and elemental carbon. Denuders can be placed in either channel or both channels. A backup filter can be placed on the denuded channel to collect volatilized particulate nitrate. Two prototype PPSS units were built and tested. The results of both laboratory testing of key PPSS components and a limited field study of the prototype in comparison to an AIHL (Air and Industrial Hygiene Laboratory) cyclone-based sampler are reported. PMID:12670062

  4. Dissolved phosphorus speciation of flash carbonization, slow pyrolysis, and fast pyrolysis biochars

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pyrolysis of waste biomass is a promising technology to produce sterile and renewable organic phosphorus fertilizers. Systematic studies are necessary to understand how different pyrolysis platforms influence the chemical speciation of dissolved (bioavailable) phosphorus. This study employed solut...

  5. Speciation of lead in contaminated soil under the influence of plants and phosphate amendment type

    NASA Astrophysics Data System (ADS)

    Diyab, C.; Juillot, F.; Dumat, C.; Morin, G.; Benedetti, M.; Mariotti, A.

    2003-05-01

    The toxicity of an element and its behaviour depend on its chemical form (speciation) and concentration. The objective of our work is to study the speciation of Pb under the influence of phosphate amendments (solide, soluble) and type of plants: peas, tomato (pH variation, organic acid complexes formation) in a polluted soil near one of Europe's largest lead contaminated area in the north of France. Chemical and physical methods were used to determine the speciation of lead in rhizospheric soil (chemical extraction, μFX, EXAFS, SEM.). The formation of lead phosphate complexe was confirmed in rhizospheric soil of both plants. Quantity and chemical structure of phosphate lead complexe formed in soil, varied with the type of plante and phosphate amendement added. Analysis of organic acids secreted by the two plantes were performed to understand the effect of organic acids on the speciation of lead in the rhizospheric soil.

  6. Speciation of triphenyltin compounds using Moessbauer spectroscopy. Final report

    SciTech Connect

    Eng, G.

    1993-11-01

    Organotin compounds have been used widely as the active agent in antifouling marine paints. Organotin compounds, i.e., tributyltin compounds (TBTs) and triphenyltin compounds (TPTs) have been found to be effective in preventing the unwanted attachment and development of aquatic organisms such as barnacles, sea grass and hydroids on ships, hulls and underwater surfaces. However, these organotin compounds have been found to be toxic to non-targeted marine species as well. While speciation of tributyltins in environmental water systems has received much attention in the literature, little information concerning the speciation of triphenyltins is found. Therefore, it would be important to study the fate of TPTs in the aquatic environment, particularly in sediments, both oxic and anoxic, in order to obtain speciation data. Since marine estuaries consist of areas with varying salinity and pH, it is important to investigate the speciation of these compounds under varying salinity conditions. In addition, evaluation of the speciation of these compounds as a function of pH would give an insight into how these compounds might interact with sediments in waters where industrial chemical run-offs can affect the pH of the estuarine environment. Finally, since organotins are present in both salt and fresh water environments, the speciation of the organotins in seawater and distilled water should also be studied. Moessbauer spectroscopy would provide a preferred method to study the speciation of triphenyltins as they leach from marine paints into the aquatic environment. Compounds used in this study are those triphenyltin compounds that are commonly incorporated into marine paints such as triphenyltin fluoride (TPTF), triphenyltin acetate (TPTOAc), triphenyltin chloride (TPTCl) and triphenyltin hydroxide (TPTOH).

  7. CORRELATING METAL SPECIATION IN SOILS

    EPA Science Inventory

    Understanding bioavailability of metals from exposure to contaminated soils is a challenging aspect of environmental research. This presentation will examine three areas of research with respect to metal speciation in soils as it relates to bioavailability: 1) Pb immobilization a...

  8. Host shift and speciation in a coral-feeding nudibranch.

    PubMed

    Faucci, Anuschka; Toonen, Robert J; Hadfield, Michael G

    2007-01-01

    While the role of host preference in ecological speciation has been investigated extensively in terrestrial systems, very little is known in marine environments. Host preference combined with mate choice on the preferred host can lead to population subdivision and adaptation leading to host shifts. We use a phylogenetic approach based on two mitochondrial genetic markers to disentangle the taxonomic status and to investigate the role of host specificity in the speciation of the nudibranch genus Phestilla (Gastropoda, Opisthobranchia) from Guam, Palau and Hawaii. Species of the genus Phestilla complete their life cycle almost entirely on their specific host coral (species of Porites, Goniopora and Tubastrea). They reproduce on their host coral and their planktonic larvae require a host-specific chemical cue to metamorphose and settle onto their host. The phylogenetic trees of the combined cytochrome oxidase I and ribosomal 16S gene sequences clarify the relationship among species of Phestilla identifying most of the nominal species as monophyletic clades. We found a possible case of host shift from Porites to Goniopora and Tubastrea in sympatric Phestilla spp. This represents one of the first documented cases of host shift as a mechanism underlying speciation in a marine invertebrate. Furthermore, we found highly divergent clades within Phestilla sp. 1 and Phestilla minor (8.1-11.1%), suggesting cryptic speciation. The presence of a strong phylogenetic signal for the coral host confirms that the tight link between species of Phestilla and their host coral probably played an important role in speciation within this genus. PMID:17134995

  9. Method for the speciation of aluminum in acidic streams

    SciTech Connect

    Miller, J.R.

    1985-01-01

    One of the impacts of acid rain falling on acid soils is the generation of high aluminum concentrations in the upper reaches of pristine mountain streams. The combination of high aluminum concentrations and lowered pH during times times of high flow is speculated by many fisheries biologists to be responsible for the decline of fish populations in these streams. In addition, this increased concern over the aquatic toxicity of aluminum has stimulated interest in the speciation of aluminum in the natural environmental. The toxicity of a metal depends greatly on its species or chemical state. The purpose of this research was to develop a practical method for speciating aluminum in those pristine streams impacted by acid rain. Aluminum has a complex chemistry involving interaction with both inorganic and organic constituents. Laboratory experiments using a chelating resin, Chelex-100, with synthetic solutions were used as the basis for speciating aluminum. The speciation procedure was applied to unfiltered samples collected from Linn Run Creek, a mildly acidic mountain stream in southwestern Pennsylvania. The results show that in upstream samples, where pH was low, rapidly exchangeable aluminum species dominated, while in the downstream samples, where pH was higher, the moderately fast exchangeable, slowly exchangeable, and inert aluminum species dominated. The laboratory experiments suggest the decline of the rapidly exchangeable fraction to be due to complexation of aluminum with humic substances. In addition, particulate aluminum was determined determined during all speciation assays.

  10. Elemental speciation analysis, from environmental to biochemical challenge

    NASA Astrophysics Data System (ADS)

    Jitaru, P.; Barbante, C.

    2006-12-01

    Information regarding the distribution of metallic/metalloid chemical species in biological compartments is required for understanding their biochemical impact on living organisms. To obtain such information implies the use of a dedicated measurement approach, namely speciation analysis. The current trend in (elemental) speciation analysis regards bioinorganic applications. New analytical methodologies are therefore necessary for identification, detection and characterization of metal(loids) complexed or incorporated into biomolecules. The established element-speciation approaches developed for the determination of low molecular mass metal(loid) species (e.g. organometallic compounds) in environmental, food, toxicological and health sciences are presently being adapted for the determination of high molecular mass metal-species, generally related to biological processes. This is one of the newest approaches in terms of element speciation and is called metallomics; this concept refers to the totality of metal species in a cell and covers the inorganic element content and the ensemble of its complexes with biomolecules, particularly proteins, participating in the organisms' response to beneficial or harmful conditions. Compared to conventional elemental speciation analysis, the approach applied to bioinorganic analysis is challenging, particularly given the difficulties in identification/characterization of the organic (e.g. protein) content of such species. In addition, quantification is not feasible with the conventional approaches, which led to the exploitation of the unique feature of (post-column) online isotope dilution-mass spectrometry for species quantification in metallomics.

  11. Sexual conflict and speciation.

    PubMed Central

    Parker, G A; Partridge, L

    1998-01-01

    We review the significance of two forms of sexual conflict (different evolutionary interests of the two sexes) for genetic differentiation of populations and the evolution of reproductive isolation. Conflicting selection on the alleles at a single locus can occur in males and females if the sexes have different optima for a trait, and there are pleiotropic genetic correlations between the sexes for it. There will then be selection for sex limitation and hence sexual dimorphism. This sex limitation could break down in hybrids and reduce their fitness. Pleiotropic genetic correlations between the sexes could also affect the likelihood of mating in interpopulation encounters. Conflict can also occur between (sex-limited) loci that determine behaviour in males and those that determine behaviour in females. Reproductive isolation may occur by rapid coevolution of male trait and female mating preference. This would tend to generate assortative mating on secondary contact, hence promoting speciation. Sexual conflict resulting from sensory exploitation, polyspermy and the cost of mating could result in high levels of interpopulation mating. If females evolve resistance to make pre- and postmating manipulation, males from one population could be more successful with females from the other, because females would have evolved resistance to their own (but not to the allopatric) males. Between-locus sexual conflict could also occur as a result of conflict between males and females of different populations over the production of unfit hybrids. We develop models which show that females are in general selected to resist such matings and males to persist, and this could have a bearing on both the initial level of interpopulation matings and the likelihood that reinforcement will occur. In effect, selection on males usually acts to promote gene flow and to restrict premating isolation, whereas selection on females usually acts in the reverse direction. We review theoretical models

  12. Trace element analytical speciation in biological systems: importance, challenges and trends

    NASA Astrophysics Data System (ADS)

    Sanz-Medel, Alfredo

    1998-02-01

    Speciation of trace elements is a relatively new field and it was in toxicology that the relationship between the chemical form of a metal and its harmful effects was first recognized. The present need for chemical speciation information in biochemistry bioinorganic and clinical chemistry is documented in an attempt to justify the present demand for innovative chemical speciation strategies and analytical technologies. The challenge and complexity of speciation is stressed and three different categories of analytical speciation of increasing analytical difficulty are proposed. Analytical strategies developed so far to try to tackle speciation problems (computational approaches, direct species-specific and hybrid techniques) are reviewed and critically assessed for biological materials. It is indisputable these days that in most cases of real-life analytical speciation we have to resort to the development and use of hybrid techniques combining an adequate separation technique for the species physical separation and an element specific detector such as those based in atomic spectrometry. Examples of such strategies, as developed mainly in the author's laboratory and including chromatographic and non-chromatographic type hybrid strategies coupled to flame, plasma and electrothermal vaporization atomic detectors, are discussed in more detail. Finally, in light of the latest trends observed in this new field, the author attempts to cast a forward look into the foreseeable future of analytical speciation research in biological and biomedical sciences. The urgent plea for quality assurance in non-routine analysis and the concept of using complementary analytical techniques and definitive methods to attack the complexity of chemical speciation in biological systems are particularly highlighted.

  13. Arsenic speciation in natural sulfidic geothermal waters

    NASA Astrophysics Data System (ADS)

    Keller, Nicole S.; Stefánsson, Andri; Sigfússon, Bergur

    2014-10-01

    The speciation of arsenic in natural sulfidic geothermal waters was studied using chemical analyses and thermodynamic aqueous speciation calculations. Samples were collected in three geothermal systems in Iceland, having contrasting H2S concentrations in the reservoir (high vs. low). The sampled waters contained 7-116 ppb As and <0.01-77.6 ppm H2S with pH of 8.56-9.60. The analytical setup used for the determination of arsenic species (Ion Chromatography-Hydride Generation Atomic Fluorescence Spectrometry, IC-HG-AFS) was field-deployed and the samples analyzed within ∼5 min of sampling in order to prevent changes upon storage, which were shown to be considerable regardless of the sample storage method used. Nine aqueous arsenic species were detected, among others arsenite (HnAsO3n-3), thioarsenite (HnAsS3n-3), arsenate (HnAsO4n-3), monothioarsenate (HnAsSO3n-3), dithioarsenate (HnAsS2O2n-3), trithioarsenate (HnAsS3O) and tetrathioarsenate (HnAsS4n-3). The results of the measured aqueous arsenic speciation in the natural geothermal waters and comparison with thermodynamic calculations reveal that the predominant factors determining the species distribution are sulfide concentration and pH. In alkaline waters with low sulfide concentrations the predominant species are AsIII oxyanions. This can be seen in samples from a liquid-only well, tapping water that is H2S-poor and free of oxygen. At intermediate sulfide concentration AsIII and AsV thio species become important and predominate at high sulfide concentration, as seen in two-phase well waters, which have high H2S concentrations in the reservoir. Upon oxidation, for instance due to mixing of the reservoir fluid with oxygenated water upon ascent to the surface, AsV oxyanions form, as well as AsV thio complexes if the sulfide concentration is intermediate to high. This oxidation process can be seen in samples from hot springs in the Geysir geothermal area. While the thermodynamic modeling allows for a first

  14. Complementary arsenic speciation methods: A review

    NASA Astrophysics Data System (ADS)

    Nearing, Michelle M.; Koch, Iris; Reimer, Kenneth J.

    2014-09-01

    The toxicity of arsenic greatly depends on its chemical form and oxidation state (speciation) and therefore accurate determination of arsenic speciation is a crucial step in understanding its chemistry and potential risk. High performance liquid chromatography with inductively coupled mass spectrometry (HPLC-ICP-MS) is the most common analysis used for arsenic speciation but it has two major limitations: it relies on an extraction step (usually from a solid sample) that can be incomplete or alter the arsenic compounds; and it provides no structural information, relying on matching sample peaks to standard peaks. The use of additional analytical methods in a complementary manner introduces the ability to address these disadvantages. The use of X-ray absorption spectroscopy (XAS) with HPLC-ICP-MS can be used to identify compounds not extracted for HPLC-ICP-MS and provide minimal processing steps for solid state analysis that may help preserve labile compounds such as those containing arsenicsbnd sulfur bonds, which can degrade under chromatographic conditions. On the other hand, HPLC-ICP-MS is essential in confirming organoarsenic compounds with similar white line energies seen by using XAS, and identifying trace arsenic compounds that are too low to be detected by XAS. The complementary use of electrospray mass spectrometry (ESI-MS) with HPLC-ICP-MS provides confirmation of arsenic compounds identified during the HPLC-ICP-MS analysis, identification of unknown compounds observed during the HPLC-ICP-MS analysis and further resolves HPLC-ICP-MS by identifying co-eluting compounds. In the complementary use of HPLC-ICP-MS and ESI-MS, HPLC-ICP-MS helps to focus the ESI-MS selection of ions. Numerous studies have shown that the information obtained from HPLC-ICP-MS analysis can be greatly enhanced by complementary approaches.

  15. Iron Speciation in Urban Dust

    SciTech Connect

    E Elzinga; Y Gao; J Fitts; R Tappero

    2011-12-31

    An improved understanding of anthropogenic impacts on ocean fertility requires knowledge of anthropogenic dust mineralogy and associated Fe speciation as a critical step toward developing Fe solubility models constrained by mineralogical composition. This study explored the utility of micro-focused X-ray absorption spectroscopy ({mu}-XAS) in characterizing the speciation of Fe in urban dust samples. A micro-focused beam of 10 x 7 {micro}m made possible the measurement of the Fe K edge XAS spectra of individual dust particles in the PM5.6 size fraction collected in Newark, New Jersey, USA. Spectral analysis indicated the presence of mixtures of Fe-containing minerals within individual dust particles; we observed significant magnetite content along with other Fe(III)-(hydr)oxide minerals which could not be conclusively identified. Our data indicate that detailed quantitative determination of Fe speciation requires extended energy scans to constrain the types and relative abundance of Fe species present. We observe heterogeneity in Fe speciation at the dust particle level, which underscores the importance of analyzing a statistically adequate number of particles within each dust sample. Where possible, {mu}-XAS measurements should be complemented with additional characterization techniques such as {mu}-XRD and bulk XAS to obtain a comprehensive picture of the Fe speciation in dust materials. X-ray microprobes should be used to complement bulk methods used to determine particle composition, methods that fail to record particle heterogeneity.

  16. Iron speciation in urban dust

    SciTech Connect

    Elzinga, E.J.; Fitts, J.; Gao, Y.; Tappero, R.

    2011-08-01

    An improved understanding of anthropogenic impacts on ocean fertility requires knowledge of anthropogenic dust mineralogy and associated Fe speciation as a critical step toward developing Fe solubility models constrained by mineralogical composition. This study explored the utility of micro-focused X-ray absorption spectroscopy ({mu}-XAS) in characterizing the speciation of Fe in urban dust samples. A micro-focused beam of 10 x 7 {mu}m made possible the measurement of the Fe K edge XAS spectra of individual dust particles in the PM5.6 size fraction collected in Newark, New Jersey, USA. Spectral analysis indicated the presence of mixtures of Fe-containing minerals within individual dust particles; we observed significant magnetite content along with other Fe(III)-(hydr)oxide minerals which could not be conclusively identified. Our data indicate that detailed quantitative determination of Fe speciation requires extended energy scans to constrain the types and relative abundance of Fe species present. We observe heterogeneity in Fe speciation at the dust particle level, which underscores the importance of analyzing a statistically adequate number of particles within each dust sample. Where possible, {mu}-XAS measurements should be complemented with additional characterization techniques such as {mu}-XRD and bulk XAS to obtain a comprehensive picture of the Fe speciation in dust materials. X-ray microprobes should be used to complement bulk methods used to determine particle composition, methods that fail to record particle heterogeneity. Keywords - Urban dust; Iron; Speciation; Micro-focused X-ray absorption spectroscopy.

  17. Metals, Health and the Environment – Emergence of Correlations Between Speciation and Effects

    PubMed Central

    Williams, David R.

    2004-01-01

    Over the last half-century both the identification of the causes of diseases and the use of inorganic compounds to treat such conditions have been considerably enlightened through our emerging capabilities to identify the pivotal chemical species involved. The ‘duty of care’ placed upon scientists to protect the environment from manufactured chemicals and to limit their effects upon humans therefrom is best realised from a speciation knowledge database. This paper discusses categorising chemicals in terms of their persistence, bioaccumulation, and toxicities and uses speciation information to optimise desirable effects of chemicals in several applications such as the manufacture of pulp for paper and in the foliar nutrition of crops. Simultaneously, the chemical wasting side effects of industrial overdosing is easily avoided if speciation approaches are used. The move towards new environmentally friendly ligand agents is described and methods of finding substitute agents (often combinations of two or more chemicals) to replace nonbiodegradable EDTA. The geosphere migration of metals through the environment is discussed in terms of speciation. Future objectives discussed include improved means of communicating speciation-based recommendations to decision makers. PMID:18365083

  18. How common is homoploid hybrid speciation?

    PubMed

    Schumer, Molly; Rosenthal, Gil G; Andolfatto, Peter

    2014-06-01

    Hybridization has long been considered a process that prevents divergence between species. In contrast to this historical view, an increasing number of empirical studies claim to show evidence for hybrid speciation without a ploidy change. However, the importance of hybridization as a route to speciation is poorly understood, and many claims have been made with insufficient evidence that hybridization played a role in the speciation process. We propose criteria to determine the strength of evidence for homoploid hybrid speciation. Based on an evaluation of the literature using this framework, we conclude that although hybridization appears to be common, evidence for an important role of hybridization in homoploid speciation is more circumscribed.

  19. Toxicity, bioavailability and metal speciation.

    PubMed

    Jonnalagadda, S B; Rao, P V

    1993-11-01

    1. Environmental toxicology emphasizes the difference from traditional toxicology in which pure compounds of interest are added to purified diets, or injected into the test animals. When the objective is to study the fate and effects of trace elements in the environment, knowledge of the speciation of the elements and their physico-chemical forms is important. 2. Cadmium salts such as the sulfides, carbonates or oxides, are practically insoluble in water. However, these can be converted to water-soluble salts in nature under the influence of oxygen and acids. Chronic exposure to Cd is associated with renal toxicity in humans once a critical body burden is reached. 3. The solubility of As(III) oxide in water is fairly low, but high in either acid or alkali. In water, arsenic is usually in the form of the arsenate or arsenite. As(III) is systemically more poisonous than the As(V), and As(V) is reduced to the As(III) form before exerting any toxic effects. Organic arsenicals also exert their toxic effects in vivo in animals by first metabolizing to the trivalent arsenoxide form. Some methyl arsenic compounds, such as di- and trimethylarsines, occur naturally as a consequence of biological activity. The toxic effect of arsenite can be potentiated by dithiols, while As has a protective effect against the toxicity of a variety of forms of Se in several species. 4. Selenium occurs in several oxidation states and many selenium analogues of organic sulfur compounds exist in nature. Selenium in selenate form occurs in alkaline soils, where it is soluble and easily available to plants. Selenite binds tightly to iron and aluminum oxides and thus is quite insoluble in soils. Hydrogen selenide is a very toxic gas at room temperature. The methylated forms of Se are much less toxic for the organism than selenite. However, the methylated Se derivatives have strong synergistic toxicity with other minerals such as arsenic. 5. Aquatic organisms absorb and retain Hg in the tissues, as

  20. Toxicity, bioavailability and metal speciation.

    PubMed

    Jonnalagadda, S B; Rao, P V

    1993-11-01

    1. Environmental toxicology emphasizes the difference from traditional toxicology in which pure compounds of interest are added to purified diets, or injected into the test animals. When the objective is to study the fate and effects of trace elements in the environment, knowledge of the speciation of the elements and their physico-chemical forms is important. 2. Cadmium salts such as the sulfides, carbonates or oxides, are practically insoluble in water. However, these can be converted to water-soluble salts in nature under the influence of oxygen and acids. Chronic exposure to Cd is associated with renal toxicity in humans once a critical body burden is reached. 3. The solubility of As(III) oxide in water is fairly low, but high in either acid or alkali. In water, arsenic is usually in the form of the arsenate or arsenite. As(III) is systemically more poisonous than the As(V), and As(V) is reduced to the As(III) form before exerting any toxic effects. Organic arsenicals also exert their toxic effects in vivo in animals by first metabolizing to the trivalent arsenoxide form. Some methyl arsenic compounds, such as di- and trimethylarsines, occur naturally as a consequence of biological activity. The toxic effect of arsenite can be potentiated by dithiols, while As has a protective effect against the toxicity of a variety of forms of Se in several species. 4. Selenium occurs in several oxidation states and many selenium analogues of organic sulfur compounds exist in nature. Selenium in selenate form occurs in alkaline soils, where it is soluble and easily available to plants. Selenite binds tightly to iron and aluminum oxides and thus is quite insoluble in soils. Hydrogen selenide is a very toxic gas at room temperature. The methylated forms of Se are much less toxic for the organism than selenite. However, the methylated Se derivatives have strong synergistic toxicity with other minerals such as arsenic. 5. Aquatic organisms absorb and retain Hg in the tissues, as

  1. Chemical speciation of uranium(VI) in marine environments: complexation of calcium and magnesium ions with [(UO2 )(CO3 )3 ](4-) and the effect on the extraction of uranium from seawater.

    PubMed

    Endrizzi, Francesco; Rao, Linfeng

    2014-10-27

    The interactions of Ca(2+) and Mg(2+) with [UO2 (CO3 )3 ](4-) were studied by calcium ion selective electrode potentiometry and spectrophotometry. The stability constants of ternary Ca-UO2 -CO3 and Mg-UO2 -CO3 complexes were determined with calcium ion selective electrode potentiometry and optical absorption spectrophotometry, respectively. The enthalpies of complexation for two successive complexes, [CaUO2 (CO3 )3 ](2-) and [Ca2 UO2 (CO3 )3 ](aq), were determined for the first time by microcalorimetry. The data help to revise the speciation of uranium(VI) species under seawater conditions. In contrast to the previously accepted assumption that the highly negatively charged [UO2 (CO3 )3 ](4-) is the dominant species, the revised speciation indicates that the dominant aqueous uranium(VI) species under seawater conditions is the neutral [Ca2 UO2 (CO3 )3 ](aq). The results have a significant impact on the strategies for developing efficient sorption processes to extract uranium from seawater. PMID:25213724

  2. NICKEL SPECIATION OF URBAN PARTICULATE MATTER

    SciTech Connect

    Kevin C. Galbreath; Charlene R. Crocker; Carolyn M. Nyberg; Frank E. Huggins; Gerald P. Huffman

    2003-10-01

    A four-step sequential Ni extraction method, summarized in Table AB-1, was evaluated for identifying and quantifying the Ni species occurring in urban total suspended particulate (TSP) matter and fine particulate matter (<10 {micro}m [PM{sub 10}] and <2.5 {micro}m [PM{sub 2.5}] in aerodynamic diameter). The extraction method was originally developed for quantifying soluble, sulfidic, elemental, and oxidic forms of Ni that may occur in industrial atmospheres. X-ray diffraction (XRD) and x-ray absorption fine structure (XAFS) spectroscopy were used to evaluate the Ni species selectivity of the extraction method. Uncertainties in the chemical speciation of Ni in urban PM{sub 10} and PM{sub 2.5} greatly affect inhalation health risk estimates, primarily because of the large variability in acute, chronic, and cancer-causing effects for different Ni compounds.

  3. Carbon speciation and surface tension of fog

    USGS Publications Warehouse

    Capel, P.D.; Gunde, R.; Zurcher, F.; Giger, W.

    1990-01-01

    The speciation of carbon (dissolved/particulate, organic/inorganic) and surface tension of a number of radiation fogs from the urban area of Zurich, Switzerland, were measured. The carbon species were dominated by "dissolved" organic carbon (DOC; i.e., the fraction that passes through a filter), which was typically present at levels of 40-200 mg/L. Less than 10% of the DOC was identified as specific individual organic compounds. Particulate organic carbon (POC) accounted for 26-41% of the mass of the particles, but usually less than 10% of the total organic carbon mass. Inorganic carbon species were relatively minor. The surface tensions of all the measured samples were less than pure water and were correlated with their DOC concentrations. The combination of high DOC and POC and low surface tension suggests a mechanism for the concentration of hydrophobic organic contaminants in the fog droplet, which have been observed by numerous investigators. ?? 1990 American Chemical Society.

  4. Plutonium speciation in water from Mono Lake, California

    USGS Publications Warehouse

    Cleveland, J.M.; Rees, T.F.; Nash, K.L.

    1983-01-01

    The solubility of plutonium in Mono Lake water is enhanced by the presence of large concentrations of indigenous carbonate ions and moderate concentrations of fluoride ions. In spite of the complex chemical composition of this water, only a few ions govern the behavior of plutonium, as demonstrated by the fact that it was possible to duplicate plutonium speciation in a synthetic water containing only the principal components of Mono Lake water.

  5. The Role of Arsenic Speciation in Dietary Exposure Assessment and the Need to Include Bioaccessibility and Biotransformation

    EPA Science Inventory

    Chemical form specific exposure assessment for arsenic has long been identified as a source of uncertainty in estimating the risk associated with the aggregate exposure for a population. Some speciation based assessments document occurrence within an exposure route; however, the...

  6. Application Of Synchrotron Techniques To Investigate In-Situ Arsenic Speciation

    EPA Science Inventory

    The speciation, or chemical form of elements governs their fate, toxicity, mobility, and bioavailability in contaminated soils, sediments and water as well as food chain transfer mechanisms. To assess these chemical properties and to accurately gauge contaminant impact on human h...

  7. SPECIATION OF GAS-PHASE AND FINE PARTICLE EMISSIONS FROM BURNING OF FOLIAR FUELS

    EPA Science Inventory

    Particle size distributions (10-1000 nm aerodynamic diameter), physical and chemical properties of fine particle matter (PM2.5) with aerodynamic diameter <2.5 micrometers, and gas-phase emissions from controlled open burning of assorted taxa were measured. Chemical speciation of ...

  8. Host shift and speciation in a coral-feeding nudibranch

    PubMed Central

    Faucci, Anuschka; Toonen, Robert J; Hadfield, Michael G

    2006-01-01

    While the role of host preference in ecological speciation has been investigated extensively in terrestrial systems, very little is known in marine environments. Host preference combined with mate choice on the preferred host can lead to population subdivision and adaptation leading to host shifts. We use a phylogenetic approach based on two mitochondrial genetic markers to disentangle the taxonomic status and to investigate the role of host specificity in the speciation of the nudibranch genus Phestilla (Gastropoda, Opisthobranchia) from Guam, Palau and Hawaii. Species of the genus Phestilla complete their life cycle almost entirely on their specific host coral (species of Porites, Goniopora and Tubastrea). They reproduce on their host coral and their planktonic larvae require a host-specific chemical cue to metamorphose and settle onto their host. The phylogenetic trees of the combined cytochrome oxidase I and ribosomal 16S gene sequences clarify the relationship among species of Phestilla identifying most of the nominal species as monophyletic clades. We found a possible case of host shift from Porites to Goniopora and Tubastrea in sympatric Phestilla spp. This represents one of the first documented cases of host shift as a mechanism underlying speciation in a marine invertebrate. Furthermore, we found highly divergent clades within Phestilla sp. 1 and Phestilla minor (8.1–11.1%), suggesting cryptic speciation. The presence of a strong phylogenetic signal for the coral host confirms that the tight link between species of Phestilla and their host coral probably played an important role in speciation within this genus. PMID:17134995

  9. Homoploid hybrid speciation in animals.

    PubMed

    Mavárez, Jesús; Linares, Mauricio

    2008-10-01

    Among animals, evidence for homoploid hybrid speciation (HHS, i.e. the creation of a hybrid lineage without a change in chromosome number) was limited until recently to the virgin chub, Gila seminuda, and some controversial data in support of hybrid status for the red wolf, Canis rufus. This scarcity of evidence, together with pessimistic attitudes among zoologists about the evolutionary importance of hybridisation, prompted the view that HHS is extremely rare among animals, especially as compared with plants. However, in recent years, the literature on animal HHS has expanded to include several new putative examples in butterflies, ants, flies and fishes. We argue that this evidence suggests that HHS is far more common than previously thought and use it to provide insights into some of the genetic and ecological aspects associated with this type of speciation among animals.

  10. 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...

  11. Variation of the NMVOC speciation in the solvent sector and the sensitivity of modelled tropospheric ozone

    NASA Astrophysics Data System (ADS)

    von Schneidemesser, E.; Coates, J.; Denier van der Gon, H. A. C.; Visschedijk, A. J. H.; Butler, T. M.

    2016-06-01

    Non-methane volatile organic compounds (NMVOCs) are detrimental to human health owing to the toxicity of many of the NMVOC species, as well as their role in the formation of secondary air pollutants such as tropospheric ozone (O3) and secondary organic aerosol. The speciation and amount of NMVOCs emitted into the troposphere are represented in emission inventories (EIs) for input to chemical transport models that predict air pollutant levels. Much of the information in EIs pertaining to speciation of NMVOCs is likely outdated, but before taking on the task of providing an up-to-date and highly speciated EI, a better understanding of the sensitivity of models to the change in NMVOC input would be highly beneficial. According to the EIs, the solvent sector is the most important sector for NMVOC emissions. Here, the sensitivity of modelled tropospheric O3 to NMVOC emission inventory speciation was investigated by comparing the maximum potential difference in O3 produced using a variety of reported solvent sector EI speciations in an idealized study using a box model. The sensitivity was tested using three chemical mechanisms that describe O3 production chemistry, typically employed for different types of modelling scales - point (MCM v3.2), regional (RADM2), and global (MOZART-4). In the box model simulations, a maximum difference of 15 ppbv (ca. 22% of the mean O3 mixing ratio of 69 ppbv) between the different EI speciations of the solvent sector was calculated. In comparison, for the same EI speciation, but comparing the three different mechanisms, a maximum difference of 6.7 ppbv was observed. Relationships were found between the relative contribution of NMVOC compound classes (alkanes and oxygenated species) in the speciations to the amount of Ox produced in the box model. These results indicate that modelled tropospheric O3 is sensitive to the speciation of NMVOCs as specified by emission inventories, suggesting that detailed updates to the EI speciation

  12. Sexual behaviour: rapid speciation in an arthropod.

    PubMed

    Mendelson, Tamra C; Shaw, Kerry L

    2005-01-27

    Theory predicts that sexual behaviour in animals can evolve rapidly, accelerating the rate of species formation. Here we estimate the rate of speciation in Laupala, a group of forest-dwelling Hawaiian crickets that is characterized primarily through differences in male courtship song. We find that Laupala has the highest rate of speciation so far recorded in arthropods, supporting the idea that divergence in courtship or sexual behaviour drives rapid speciation in animals.

  13. Speciation of Fe in ambient aerosol and cloudwater

    SciTech Connect

    Siefert, L.

    1996-08-15

    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 worlds 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.

  14. Geochemical Speciation Mass Transfer

    1985-12-01

    PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineralmore » phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.« less

  15. ACTRIS ACSM intercomparison - Part I: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with Time-of-Flight ACSM (ToF-ACSM), High Resolution ToF Aerosol Mass Spectrometer (HR-ToF-AMS) and other co-located instruments

    NASA Astrophysics Data System (ADS)

    Crenn, V.; Sciare, J.; Croteau, P. L.; Verlhac, S.; Fröhlich, R.; Belis, C. A.; Aas, W.; Äijälä, M.; Alastuey, A.; Artiñano, B.; Baisnée, D.; Bonnaire, N.; Bressi, M.; Canagaratna, M.; Canonaco, F.; Carbone, C.; Cavalli, F.; Coz, E.; Cubison, M. J.; Esser-Gietl, J. K.; Green, D. C.; Gros, V.; Heikkinen, L.; Herrmann, H.; Lunder, C.; Minguillón, M. C.; Močnik, G.; O'Dowd, C. D.; Ovadnevaite, J.; Petit, J.-E.; Petralia, E.; Poulain, L.; Priestman, M.; Riffault, V.; Ripoll, A.; Sarda-Estève, R.; Slowik, J. G.; Setyan, A.; Wiedensohler, A.; Baltensperger, U.; Prévôt, A. S. H.; Jayne, J. T.; Favez, O.

    2015-07-01

    As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for three weeks during the late fall-early winter period (November-December 2013). The first week was dedicated to tuning and calibration of each instrument whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual ACSM across all chemical families except for chloride for which three ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025) and were found to be of 9, 15, 19, 28 and 36 % for NR-PM1, nitrate, organic matter, sulfate and ammonium respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of ACSMs, detailed intercomparison results are presented as well as a discussion of some recommendations

  16. Daily Rhythm of Mutualistic Pollinator Activity and Scent Emission in Ficus septica: Ecological Differentiation between Co-Occurring Pollinators and Potential Consequences for Chemical Communication and Facilitation of Host Speciation

    PubMed Central

    Conchou, Lucie; Cabioch, Léa; Rodriguez, Lillian J. V.; Kjellberg, Finn

    2014-01-01

    The mutualistic interaction between Ficus and their pollinating agaonid wasps constitutes an extreme example of plant-insect co-diversification. Most Ficus species are locally associated with a single specific agaonid wasp species. Specificity is ensured by each fig species emitting a distinctive attractive scent. However, cases of widespread coexistence of two agaonid wasp species on the same Ficus species are documented. Here we document the coexistence of two agaonid wasp species in Ficus septica: one yellow-colored and one black-colored. Our results suggest that their coexistence is facilitated by divergent ecological traits. The black species is longer-lived (a few more hours) and is hence active until later in the afternoon. Some traits of the yellow species must compensate for this advantage for their coexistence to be stable. In addition, we show that the composition of the scent emitted by receptive figs changes between sunrise and noon. The two species may therefore be exposed to somewhat different ranges of receptive fig scent composition and may consequently diverge in the way they perceive and/or respond to scents. Whether such situations may lead to host plant speciation is an open question. PMID:25105796

  17. Mercury speciation in floodplain soils and sediments along a contaminated river transect

    SciTech Connect

    Wallschlaeger, D.; Desai, M.V.M.; Spengler, M.; Wilken, R.D.

    1998-09-01

    A novel mercury-specific sequential extraction procedure (SEP) for the assessment of mercury (Hg) speciation in soils and sediments, with emphasis on studying the interaction between Hg and organic matter (OM), was developed and tested. It was applied to determine Hg speciation in floodplain topsoils and surface sediments along the Hg-contaminated part of the river Elbe, and to simultaneously derive some information on the (re)mobilization potentials for Hg from these matrices. The majority of the total Hg in the ecosystem today is bound in the floodplains, which also still geographically reflect the historic emission record. Most of the Hg in both matrices is bound strongly to OM, suggesting low availability. However, distinct differences between Hg speciation in the floodplain soils and sediments were also discovered. Mercury deposited in the floodplains shows speciation patterns that indicate stronger fixation compared with Hg in the sediments. This difference is attributed to the association of Hg with larger quantities of OM, which presumably also has higher molecular weight (MW). By comparison, Hg in the sediments was distributed among weaker binding forms, which are more likely to liberate Hg. Particularly, sediments showed a total lack of sulfidic binding forms for Hg. Pronounced geographical trends were detected in the Hg speciation along the river transect, with a general downstream shift from weaker to stronger binding forms, probably due to increased association with OM. These studies indicate that Hg speciation in riverine ecosystems is dynamic and reflects the chemical mechanisms underlying (bio) geochemical processes like distribution and transport.

  18. Arsenic speciation in edible mushrooms.

    PubMed

    Nearing, Michelle M; Koch, Iris; Reimer, Kenneth J

    2014-12-16

    The fruiting bodies, or mushrooms, of terrestrial fungi have been found to contain a high proportion of the nontoxic arsenic compound arsenobetaine (AB), but data gaps include a limited phylogenetic diversity of the fungi for which arsenic speciation is available, a focus on mushrooms with higher total arsenic concentrations, and the unknown formation and role of AB in mushrooms. To address these, the mushrooms of 46 different fungus species (73 samples) over a diverse range of phylogenetic groups were collected from Canadian grocery stores and background and arsenic-contaminated areas. Total arsenic was determined using ICP-MS, and arsenic speciation was determined using HPLC-ICP-MS and complementary X-ray absorption spectroscopy (XAS). The major arsenic compounds in mushrooms were found to be similar among phylogenetic groups, and AB was found to be the major compound in the Lycoperdaceae and Agaricaceae families but generally absent in log-growing mushrooms, suggesting the microbial community may influence arsenic speciation in mushrooms. The high proportion of AB in mushrooms with puffball or gilled morphologies may suggest that AB acts as an osmolyte in certain mushrooms to help maintain fruiting body structure. The presence of an As(III)-sulfur compound, for the first time in mushrooms, was identified in the XAS analysis. Except for Agaricus sp. (with predominantly AB), inorganic arsenic predominated in most of the store-bought mushrooms (albeit with low total arsenic concentrations). Should inorganic arsenic predominate in these mushrooms from contaminated areas, the risk to consumers under these circumstances should be considered.

  19. 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

  20. Speciation in fungal and oomycete plant pathogens

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The process of speciation by definition involves evolution of one or more reproductive isolating mechanisms that split a single species into two that can no longer interbreed. Determination of which processes are responsible for speciation is important yet challenging. Several studies have proposed ...

  1. Speciation genetics: current status and evolving approaches.

    PubMed

    Wolf, Jochen B W; Lindell, Johan; Backström, Niclas

    2010-06-12

    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.

  2. Advances in Ecological Speciation: an integrative approach.

    PubMed

    Faria, Rui; Renaut, Sebastien; Galindo, Juan; Pinho, Catarina; Melo-Ferreira, José; Melo, Martim; Jones, Felicity; Salzburger, Walter; Schluter, Dolph; Butlin, Roger

    2014-02-01

    The role of natural selection in promoting reproductive isolation has received substantial renewed interest within the last two decades. As a consequence, the study of ecological speciation has become an extremely productive research area in modern evolutionary biology. Recent innovations in sequencing technologies offer an unprecedented opportunity to study the mechanisms involved in ecological speciation. Genome scans provide significant insights but have some important limitations; efforts are needed to integrate them with other approaches to make full use of the sequencing data deluge. An international conference 'Advances in Ecological Speciation' organized by the University of Porto (Portugal) aimed to review current progress in ecological speciation. Using some of the examples presented at the conference, we highlight the benefits of integrating ecological and genomic data and discuss different mechanisms of parallel evolution. Finally, future avenues of research are suggested to advance our knowledge concerning the role of natural selection in the establishment of reproductive isolation during ecological speciation.

  3. Rates of speciation in the fossil record

    NASA Technical Reports Server (NTRS)

    Sepkoski, J. J. Jr; Sepkoski JJ, J. r. (Principal Investigator)

    1998-01-01

    Data from palaeontology and biodiversity suggest that the global biota should produce an average of three new species per year. However, the fossil record shows large variation around this mean. Rates of origination have declined through the Phanerozoic. This appears to have been largely a function of sorting among higher taxa (especially classes), which exhibit characteristic rates of speciation (and extinction) that differ among them by nearly an order of magnitude. Secular decline of origination rates is hardly constant, however; many positive deviations reflect accelerated speciation during rebounds from mass extinctions. There has also been general decline in rates of speciation within major taxa through their histories, although rates have tended to remain higher among members in tropical regions. Finally, pulses of speciation appear sometimes to be associated with climate change, although moderate oscillations of climate do not necessarily promote speciation despite forcing changes in species' geographical ranges.

  4. Rates of speciation in the fossil record.

    PubMed Central

    Sepkoski, J J

    1998-01-01

    Data from palaeontology and biodiversity suggest that the global biota should produce an average of three new species per year. However, the fossil record shows large variation around this mean. Rates of origination have declined through the Phanerozoic. This appears to have been largely a function of sorting among higher taxa (especially classes), which exhibit characteristic rates of speciation (and extinction) that differ among them by nearly an order of magnitude. Secular decline of origination rates is hardly constant, however; many positive deviations reflect accelerated speciation during rebounds from mass extinctions. There has also been general decline in rates of speciation within major taxa through their histories, although rates have tended to remain higher among members in tropical regions. Finally, pulses of speciation appear sometimes to be associated with climate change, although moderate oscillations of climate do not necessarily promote speciation despite forcing changes in species' geographical ranges. PMID:11541734

  5. 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...

  6. Environmental harshness, latitude and incipient speciation.

    PubMed

    Weir, Jason T

    2014-02-01

    Are rates of evolution and speciation fastest where diversity is greatest - the tropics? A commonly accepted theory links the latitudinal diversity gradient to a speciation pump model whereby the tropics produce species at a faster rate than extra-tropical regions. In this issue of Molecular Ecology, Botero et al. () test the speciation pump model using subspecies richness patterns for more than 9000 species of birds and mammals as a proxy for incipient speciation opportunity. Rather than using latitudinal centroids, the authors investigate the role of various environmental correlates of latitude as drivers of subspecies richness. Their key finding points to environmental harshness as a positive predictor of subspecies richness. The authors link high subspecies richness in environmental harsh areas to increased opportunities for geographic range fragmentation and/or faster rates of trait evolution as drivers of incipient speciation. Because environmental harshness generally increases with latitude, these results suggest that opportunity for incipient speciation is lowest where species richness is highest. The authors interpret this finding as incompatible with the view of the tropics as a cradle of diversity. Their results are consistent with a growing body of evidence that reproductive isolation and speciation occur fastest at high latitudes. PMID:26010836

  7. Genomic divergence during speciation: causes and consequences

    PubMed Central

    Nosil, Patrik; Feder, Jeffrey L.

    2012-01-01

    Speciation is a fundamental process responsible for the diversity of life. Progress has been made in detecting individual ‘speciation genes’ that cause reproductive isolation. In contrast, until recently, less attention has been given to genome-wide patterns of divergence during speciation. Thus, major questions remain concerning how individual speciation genes are arrayed within the genome, and how this affects speciation. This theme issue is dedicated to exploring this genomic perspective of speciation. Given recent sequencing and computational advances that now allow genomic analyses in most organisms, the goal is to help move the field towards a more integrative approach. This issue draws upon empirical studies in plants and animals, and theoretical work, to review and further document patterns of genomic divergence. In turn, these studies begin to disentangle the role that different processes, such as natural selection, gene flow and recombination rate, play in generating observed patterns. These factors are considered in the context of how genomes diverge as speciation unfolds, from beginning to end. The collective results point to how experimental work is now required, in conjunction with theory and sequencing studies, to move the field from descriptive studies of patterns of divergence towards a predictive framework that tackles the causes and consequences of genome-wide patterns. PMID:22201163

  8. Drift promotes speciation by sexual selection.

    PubMed

    Uyeda, Josef C; Arnold, Stevan J; Hohenlohe, Paul A; Mead, Louise S

    2009-03-01

    Quantitative genetic models of sexual selection have generally failed to provide a direct connection to speciation and to explore the consequences of finite population size. The connection to speciation has been indirect because the models have treated only the evolution of male and female traits and have stopped short of modeling the evolution of sexual isolation. In this article we extend Lande's (1981) model of sexual selection to quantify predictions about the evolution of sexual isolation and speciation. Our results, based on computer simulations, support and extend Lande's claim that drift along a line of equilibria can rapidly lead to sexual isolation and speciation. Furthermore, we show that rapid speciation can occur by drift in populations of appreciable size (N(e) >or= 1000). These results are in sharp contrast to the opinion of many researchers and textbook writers who have argued that drift does not play an important role in speciation. We argue that drift may be a powerful amplifier of speciation under a wide variety of modeling assumptions, even when selection acts directly on female mating preferences.

  9. The biological speciation and toxicokinetics of aluminum.

    PubMed Central

    DeVoto, E; Yokel, R A

    1994-01-01

    This review discusses recent literature on the chemical and physiological factors that influence the absorption, distribution, and excretion of aluminum in mammals, with particular regard to gastrointestinal absorption and speciation in plasma. Humans encounter aluminum, a ubiquitous yet highly insoluble element in most forms, in foods, drinking water, and pharmaceuticals. Exposure also occurs by inhalation of dust and aerosols, particularly in occupational settings. Absorption from the gut depends largely on pH and the presence of complexing ligands, particularly carboxylic acids, with which the metal can form absorbable neutral aluminum species. Uremic animals and humans experience higher than normal body burdens of aluminum despite increased urinary clearance of the metal. In plasma, 80-90% of aluminum binds to transferrin, an iron-transport protein for which receptors exist in many tissue. The remaining fraction of plasma aluminum takes the form of small-molecule hydroxy species and small complexes with carboxylic acids, phosphate, and, to a much lesser degree, amino acids. Most of these species have not been observed in vivo but are predicted from equilibrium models derived from potentiometric methods and NMR investigations. These models predict that the major small-molecule aluminum species under plasma conditions are charged and hence unavailable for uptake into tissues. PMID:9738208

  10. Fe, Ni and Zn speciation, in airborne particulate matter

    NASA Astrophysics Data System (ADS)

    Thiodjio Sendja, Bridinette; Aquilanti, Giuliana; Vassura, Ivano; Giorgetti, Marco

    2016-05-01

    The study of elemental speciation in atmospheric particulate matter is important for the assessment of the source of the particle as well for the evaluation of its toxicity. XANES data at Fe, Ni, and Zn K-edges are recorded on a sample of urban dust (from the Rimini area of Emilia Romagna region, Italy) deposited on a filter and on the NIST standard reference material 1648. Using linear combination fitting we give an indication of the chemical species of the three metals present in the samples.

  11. EFFECTS OF IRON CONTENT IN COAL COMBUSTION FLY ASHES ON SPECIATION OF MERCURY

    EPA Science Inventory

    The paper discusses the effects of iron content in coal combustion fly ashes on speciation of mercury. (NOTE: The chemical form of mercury species in combustion flue gases is an important influence on the control of mercury emissions from coal combustion). The study focused on th...

  12. Arsenic speciation and reactivity in poultry litter

    USGS Publications Warehouse

    Arai, Y.; Lanzirotti, A.; Sutton, S.; Davis, J.A.; Sparks, D.L.

    2003-01-01

    Recent U.S. government action to lower the maximum concentration levels (MCL) of total arsenic (As) (10 ppb) in drinking water has raised serious concerns about the agricultural use of As-containing biosolids such as poultry litter (PL). In this study, solid-state chemical speciation, desorbability, and total levels of As in PL and long-term amended soils were investigated using novel synchrotronbased probing techniques (microfocused (??) synchrotron X-ray fluorescence (SXRF) and ??-X-ray absorption near-edge structure (XANES) spectroscopies) coupled with chemical digestion and batch experiments. The total As levels in the PL were as high as ???50 mg kg-1, and As(II/III and V) was always concentrated in abundant needle-shaped microscopic particles (???20/ ??m x 850 ??m) associated with Ca, Cu, and Fe and to a lesser extent with S, CI, and Zn. Postedge XANES features of litter particles are dissimilar to those of the organo-As(V) compound in poultry feed (i.e., roxarsone), suggesting possible degradation/transformation of roxarsone in the litter and/or in poultry digestive tracts. The extent of As desorption from the litter increased with increasing time and pH from 4.5 to 7, but at most 15% of the total As was released after 5 d at pH 7, indicating the presence of insoluble phases and/or strongly retained soluble compounds. No significant As accumulation (< 15 mg kg-1) was found in long-term PL-a mended agricultural surface soils. This suggests that As in the PL may have undergone surface and subsurface transport processes. Our research results raise concerns about long-term PL amendment effects on As contamination in surrounding soilwater environments.

  13. Speciation: Genomic Archipelagos in a Crater Lake.

    PubMed

    Ronco, Fabrizia; Salzburger, Walter

    2016-03-01

    The opening stages of speciation remain poorly understood, especially from a genomic perspective. The genomes of newly discovered crater-lake cichlid fish shed light on the early phases of diversification and suggest that selection acts on multiple genomic regions.

  14. CORRELATING METAL SPECIATION IN SOILS TO RISK

    EPA Science Inventory

    Understanding bioavailability of metals from exposure to contaminated soils is a challenging aspect of environmental research. This presentation will examine three areas of research with respect to metal speciation in soils as it relates to bioavailability: 1) Pb immobilization a...

  15. Speciation And Colloid Transport of Arsenic From Mine Tailings

    SciTech Connect

    Slowey, A.J.; Johnson, S.B.; Newville, M.; Brown, G.E., Jr.

    2007-07-13

    In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d{sup -1} through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe{sub 3}(SO{sub 4}, AsO{sub 4}){sub 2}(OH){sub 6}] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 {micro}m mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.

  16. Using Visible Spectrophotometers and pH Measurements to Study Speciation in a Guided-Inquiry Laboratory

    ERIC Educational Resources Information Center

    Otto, William H.; Larive, Cynthia K.; Mason, Susan L.; Robinson, Janet B.; Heppert Joseph A.; Ellis, James D.

    2005-01-01

    An experiment to perform a simple initial investigation that illustrates concepts of speciation and equilibrium, using the instrument and chemical resources in the laboratory is presented. The investigation showed that the presence of multiple chemical species in a reaction mixture (phenol red solution) reflects the acid and base conditions…

  17. Dualism and conflicts in understanding speciation.

    PubMed

    Schilthuizen, M

    2000-12-01

    Speciation is a central but elusive issue in evolutionary biology. Over the past sixty years, the subject has been studied within a framework conceived by Ernst Mayr and Theodosius Dobzhansky and subsequently developed further by numerous other workers. In this "isolation" theory, the evolution of reproductive isolation is a key element of speciation; natural selection is given only secondary importance while gene flow is considered prohibitive to the process. In this paper, I argue that certain elements in this approach have produced confusion and irreconcilability among students of speciation. The more prominent debates in speciation (i.e., the species definition, sympatry/allopatry, and the role of reinforcement) all derive from an inherent conflict between the "isolation" theory and Darwin's "selection" view on species and speciation (in which disruptive selection is crucial). New data, mainly from field ecology, molecular population genetics, laboratory studies with Drosophila and computer analysis, all suggest that the isolation theory may no longer be the most desirable vantage point from which to explore speciation. Instead, environmental selection in large populations, often unimpeded by ongoing gene flow, appears to be the decisive element. The traditional preoccupation with reproductive isolation has created gaps in our knowledge of several crucial issues, mainly regarding the role of environmental selection and its connection with mate selection.

  18. NMR studies of copper speciation in the bovine rumen environment.

    PubMed

    Reid, R S; Attaelmannan, M A

    1998-02-01

    Dietary copper supplements containing complexed copper have been asserted to be more bioavailable than 'inorganic' supplements. Since bioavailability is intimately related to the particular metal ion species that exist in any given environment, studies of solution speciation can be used to examine this assertion. In a previous study, our computer modeling of copper speciation in bovine saliva indicated that when a lysine-complexed copper supplement is used, the complex will not persist. In the present study, these conclusions are supplemented and extended using 1H NMR experiments. Lysine and the copper(II)-lysine system are characterized, and chemical shifts of the individual species obtained. Chemical shift values for the copper(II)-lysine-bovine saliva system can then be predicted. Results show good agreement with experimental values. The scope of the computer modeling is then expanded to include the major low molar mass ligands present in the rumen. Implications of the results are discussed. The validity of this rumen model is further evaluated by NMR investigations on biological samples. The study provides further evidence that complexes such as copper(II)-lysine would disintegrate in the gastrointestinal tract, and are unlikely to be absorbed intact.

  19. Ecological speciation in marine v. freshwater fishes.

    PubMed

    Puebla, O

    2009-10-01

    Absolute barriers to dispersal are not common in marine systems, and the prevalence of planktonic larvae in marine taxa provides potential for gene flow across large geographic distances. These observations raise the fundamental question in marine evolutionary biology as to whether geographic and oceanographic barriers alone can account for the high levels of species diversity observed in marine environments such as coral reefs, or whether marine speciation also operates in the presence of gene flow between diverging populations. In this respect, the ecological hypothesis of speciation, in which reproductive isolation results from divergent or disruptive natural selection, is of particular interest because it may operate in the presence of gene flow. Although important insights into the process of ecological speciation in aquatic environments have been provided by the study of freshwater fishes, comparatively little is known about the possibility of ecological speciation in marine teleosts. In this study, the evidence consistent with different aspects of the ecological hypothesis of speciation is evaluated in marine fishes. Molecular approaches have played a critical role in the development of speciation hypotheses in marine fishes, with a role of ecology suggested by the occurrence of sister clades separated by ecological factors, rapid cladogenesis or the persistence of genetically and ecologically differentiated species in the presence of gene flow. Yet, ecological speciation research in marine fishes is still largely at an exploratory stage. Cases where the major ingredients of ecological speciation, namely a source of natural divergent or disruptive selection, a mechanism of reproductive isolation and a link between the two have been explicitly documented are few. Even in these cases, specific predictions of the ecological hypothesis of speciation remain largely untested. Recent developments in the study of freshwater fishes illustrate the potential for

  20. Mixed 3d/4f polynuclear complexes with 2,2‧-oxydiacetate as bridging ligand: Synthesis, structure and chemical speciation of La M compounds (M = bivalent cation)

    NASA Astrophysics Data System (ADS)

    Domínguez, Sixto; Torres, Julia; Peluffo, Florencia; Mederos, Alfredo; González-Platas, Javier; Castiglioni, Jorge; Kremer, Carlos

    2007-03-01

    Heterometallic compounds containing La(III), bivalent cations M (M = Co, Ni, Ca), and 2,2‧-oxydiacetate (oda) as connecting ligand have been prepared and characterized. The complexes can be formulated as [La2M3(oda)6(H2O)6] · 12H2O. The structure of [La2Co3(oda)6(H2O)6] shows the presence of the La(III) coordinated by six carboxy and three ether oxygen atoms, and the Co(II) cation bonded to four carboxy oxygens and two molecules of water. An open 3D framework is observed, containing large hexagonal channels. The chemical systems were also investigated in solution (25.0 °C, I = 0.5 M Me4NCl) by potentiometry. The same kind of polynuclear species have been found in aqueous solution.

  1. Investigation of copper speciation in pig slurry by a multitechnique approach.

    PubMed

    Legros, Samuel; Chaurand, Perrine; Rose, Jérôme; Masion, Armand; Briois, Valérie; Ferrasse, Jean-Henry; Macary, Hervé Saint; Bottero, Jean-Yves; Doelsch, Emmanuel

    2010-09-15

    It is now well-known that copper (Cu) can accumulate on the surface of soils upon which pig slurry has been applied. This is due to the high quantity of Cu in pig slurry resulting from its use as a growth promoter in animal feeds. The mobility and bioavailability of Cu from pig slurry spreading can be better predicted by determining the speciation of this element in addition to its total concentration. The aim of this study was to present a multitechnique approach to investigate Cu speciation in pig slurry. First, size fractionation and chemical characterization of each size fraction were performed to complement results obtained in raw samples. Micro X-ray fluorescence spectroscopy (μXRF) highlighted the colocalization of Cu and sulfur (S). Finally, X-ray absorption near-edge structure spectroscopy (XANES) showed that Cu speciation in raw pig slurry and size fractions could be described by Cu(2)S and that its oxidation state is Cu(I). In addition, geochemical calculation demonstrated that chalcocite (Cu(2)S) was the major Cu species present under pig slurry lagoon physical-chemical conditions. This Cu speciation in pig slurry may be the main reason for the observed Cu accumulation at the soil surface. PMID:20735047

  2. Speciation without Pre-Defined Fitness Functions

    PubMed Central

    Gras, Robin; Golestani, Abbas; Hendry, Andrew P.; Cristescu, Melania E.

    2015-01-01

    The forces promoting and constraining speciation are often studied in theoretical models because the process is hard to observe, replicate, and manipulate in real organisms. Most models analyzed to date include pre-defined functions influencing fitness, leaving open the question of how speciation might proceed without these built-in determinants. To consider the process of speciation without pre-defined functions, we employ the individual-based ecosystem simulation platform EcoSim. The environment is initially uniform across space, and an evolving behavioural model then determines how prey consume resources and how predators consume prey. Simulations including natural selection (i.e., an evolving behavioural model that influences survival and reproduction) frequently led to strong and distinct phenotypic/genotypic clusters between which hybridization was low. This speciation was the result of divergence between spatially-localized clusters in the behavioural model, an emergent property of evolving ecological interactions. By contrast, simulations without natural selection (i.e., behavioural model turned off) but with spatial isolation (i.e., limited dispersal) produced weaker and overlapping clusters. Simulations without natural selection or spatial isolation (i.e., behaviour model turned off and high dispersal) did not generate clusters. These results confirm the role of natural selection in speciation by showing its importance even in the absence of pre-defined fitness functions. PMID:26372462

  3. Accelerated speciation in colour-polymorphic birds.

    PubMed

    Hugall, Andrew F; Stuart-Fox, Devi

    2012-05-09

    Colour polymorphism exemplifies extreme morphological diversity within populations. It is taxonomically widespread but generally rare. Theory suggests that where colour polymorphism does occur, processes generating and maintaining it can promote speciation but the generality of this claim is unclear. Here we confirm, using species-level molecular phylogenies for five families of non-passerine birds, that colour polymorphism is associated with accelerated speciation rates in the three groups in which polymorphism is most prevalent. In all five groups, colour polymorphism is lost at a significantly greater rate than it is gained. Thus, the general rarity and phylogenetic dispersion of colour polymorphism is accounted for by a combination of higher speciation rate and higher transition rate from polymorphism to monomorphism, consistent with theoretical models where speciation is driven by fixation of one or more morphs. This is corroborated by evidence from a species-level molecular phylogeny of passerines, incorporating 4,128 (66.5%) extant species, that polymorphic species tend to be younger than monomorphic species. Our results provide empirical support for the general proposition, dating from classical evolutionary theory, that colour polymorphism can increase speciation rates.

  4. Speciation by Symbiosis: the Microbiome and Behavior

    PubMed Central

    Shropshire, J. Dylan

    2016-01-01

    ABSTRACT Species are fundamental units of comparison in biology. The newly discovered importance and ubiquity of host-associated microorganisms are now stimulating work on the roles that microbes can play in animal speciation. We previously synthesized the literature and advanced concepts of speciation by symbiosis with notable attention to hybrid sterility and lethality. Here, we review recent studies and relevant data on microbes as players in host behavior and behavioral isolation, emphasizing the patterns seen in these analyses and highlighting areas worthy of additional exploration. We conclude that the role of microbial symbionts in behavior and speciation is gaining exciting traction and that the holobiont and hologenome concepts afford an evolving intellectual framework to promote research and intellectual exchange between disciplines such as behavior, microbiology, genetics, symbiosis, and speciation. Given the increasing centrality of microbiology in macroscopic life, microbial symbiosis is arguably the most neglected aspect of animal and plant speciation, and studying it should yield a better understanding of the origin of species. PMID:27034284

  5. Hydroxyl speciation in felsic magmas

    NASA Astrophysics Data System (ADS)

    Malfait, Wim J.; Xue, Xianyu

    2014-09-01

    The hydroxyl speciation of hydrous, metaluminous potassium and calcium aluminosilicate glasses was investigated by 27Al-1H cross polarization and quantitative 1H MAS NMR spectroscopy. Al-OH is present in both the potassium and the calcium aluminosilicate glasses and its 1H NMR partial spectrum was derived from the 27Al-1H cross polarization data. For the calcium aluminosilicate glasses, the abundance of Al-OH could not be determined because of the low spectral resolution. For the potassium aluminosilicate glasses, the fraction of Al-OH was quantified by fitting its partial spectrum to the quantitative 1H NMR spectra. The degree of aluminum avoidance and the relative tendency for Si-O-Si, Si-O-Al and Al-O-Al bonds to hydrolyze were derived from the measured species abundances. Compared to the sodium, lithium and calcium systems, potassium aluminosilicate glasses display a much stronger degree of aluminum avoidance and a stronger tendency for the Al-O-Al linkages to hydrolyze. Combining our results with those for sodium aluminosilicate glasses (Malfait and Xue, 2010a), we predict that the hydroxyl groups in rhyolitic and phonolitic magmas are predominantly present as Si-OH (84-89% and 68-78%, respectively), but with a significant fraction of Al-OH (11-16% and 22-32%, respectively). For both rhyolitic and phonolitic melts, the AlOH/(AlOH + SiOH) ratio is likely smaller than the Al/(Al + Si) ratio for the lower end of the natural temperature range but may approach the Al/(Al + Si) ratio at higher temperatures.

  6. Speciation along a depth gradient in a marine adaptive radiation

    PubMed Central

    Ingram, Travis

    2011-01-01

    Oceans are home to much of the world's biodiversity, but we know little about the processes driving speciation in marine ecosystems with few geographical barriers to gene flow. Ecological speciation resulting from divergent natural selection between ecological niches can occur in the face of gene flow. Sister species in the young and ecologically diverse rockfish genus Sebastes coexist in the northeast Pacific, implying that speciation may not require geographical isolation. Here, I use a novel phylogenetic comparative analysis to show that rockfish speciation is instead associated with divergence in habitat depth and depth-associated morphology, consistent with models of parapatric speciation. Using the same analysis, I find no support for alternative hypotheses that speciation involves divergence in diet or life history, or that speciation involves geographic isolation by latitude. These findings support the hypothesis that rockfishes undergo ecological speciation on an environmental gradient. PMID:20810434

  7. Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff.

    PubMed

    Zuo, Xiaojun; Fu, Dafang; Li, He

    2012-11-01

    Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.

  8. Ecology: is speciation driven by species diversity?

    PubMed

    Cadena, Carlos Daniel; Ricklefs, Robert E; Jiménez, Iván; Bermingham, Eldredge

    2005-11-01

    Emerson and Kolm show that the proportion of species endemic to an island is positively related to its species richness and, assuming that endemism indexes speciation rate, they infer that greater species diversity accelerates diversification. Here we demonstrate that the same correlation between species richness and percentage endemism can arise even if within-island speciation is negligible, particularly when both endemism and species richness depend on attributes of islands (such as area) that influence the average age of resident populations. Island biogeography theory indicates that, where the average time to extinction is relatively long, diversity increases through colonization, irrespective of whether new species are formed; at the same time, islands on which populations persist for longer accumulate more endemic species as local populations differentiate and populations on neighbouring islands become extinct. We therefore suggest that species richness and endemism are correlated fortuitously owing to their mutual dependence on the life spans of populations on islands, which is unrelated to speciation itself.

  9. Evidence for ecology's role in speciation.

    PubMed

    McKinnon, Jeffrey S; Mori, Seiichi; Blackman, Benjamin K; David, Lior; Kingsley, David M; Jamieson, Leia; Chou, Jennifer; Schluter, Dolph

    2004-05-20

    A principal challenge in testing the role of natural selection in speciation is to connect the build-up of reproductive isolation between populations to divergence of ecologically important traits. Demonstrations of 'parallel speciation', or assortative mating by selective environment, link ecology and isolation, but the phenotypic traits mediating isolation have not been confirmed. Here we show that the parallel build-up of mating incompatibilities between stickleback populations can be largely accounted for by assortative mating based on one trait, body size, which evolves predictably according to environment. In addition to documenting the influence of body size on reproductive isolation for stickleback populations spread across the Northern Hemisphere, we have confirmed its importance through a new experimental manipulation. Together, these results suggest that speciation may arise largely as a by-product of ecological differences and divergent selection on a small number of phenotypic traits. PMID:15152252

  10. [XANES study of lead speciation in duckweed].

    PubMed

    Chu, Bin-Bin; Luo, Li-Qiang; Xu, Tao; Yuan, Jing; Sun, Jian-Ling; Zeng, Yuan; Ma, Yan-Hong; Yi, Shan

    2012-07-01

    Qixiashan lead-zinc mine of Nanjing was one of the largest lead zinc deposits in East China Its exploitation has been over 50 years, and the environmental pollution has also been increasing. The lead concentration in the local environment was high, but lead migration and toxic mechanism has not been clear. Therefore, biogeochemistry research of the lead zinc mine was carried out. Using ICP-MS and Pb-L III edge XANES, lead concentration and speciation were analyzed respectively, and duckweed which can tolerate and enriched heavy metals was found in the pollution area. The results showed that the lead concentration of duckweed was 39.4 mg x kg(-1). XANES analysis and linear combination fit indicated that lead stearate and lead sulfide accounted for 65% and 36.9% respectively in the lead speciation of duckweed, suggesting that the main lead speciation of duckweed was sulfur-containing lead-organic acid.

  11. [Speciation of metals in occupational medicine].

    PubMed

    Apostoli, P

    1998-01-01

    The identification and quantification of elements as such (that make up the historical analytical method used in toxicological studies) are necessary but not sufficient, in all cases, to understand and evaluate the mechanism of interaction between elements and biological targets. In fact, in order to approximate the factors that control the concentrations of elements in environmental or biological media, we need to know the occurrence of species of the elements themselves. This is element speciation, i.e. the capability of separating, identifying and determining the species in which an element is present and/or transformed. There are few, although increasing in latter years, examples of element speciation able to confirm the importance of this research approach in toxicological studies. Some basic information from these studies have found specific application in selecting the most appropriate indicators and the most representative matrices for biological monitoring. Furthermore, element speciation provides additional and often essential information in evaluating metal toxicity. The toxicity of the three oxidation states of Mercury differ considerably. For arsenic, a decreasing order of toxicity arsenite > arsenate > monomethylarsonic (MMA) > dimethylarsenite (DMA) has been proposed. However, the use of speciation in investigating toxicokinetic aspects appears to be difficult to apply to many other metals, mainly due to the lack of information about the existence and significance of species whose determination would be worthwhile and to the lack of analytical methods enabling us to measure species in biological media. Nonetheless, the horizon for speciation is more extensive and less linear than expected since about 15 elements, 20 oxidation states, and 25 organic compounds have been just involved in speciation. Problems might arise for biological monitoring practices, and the following topics should be considered: (i) identification of species and determination of

  12. Dynamic of lead speciation in sewage sludge composting.

    PubMed

    Zheng, G D; Chen, T B; Gao, D; Luo, W

    2004-01-01

    A large-scale sewage sludge composting experiment was conducted to develop an understanding of changes that occur to Pb chemical speciation, distribution and bio-availability during the course of composting. The four-stage Tessier sequential extraction method was employed to investigate the dynamics of heavy metal Pb speciation (exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and sulphides, residual) during the course of sewage sludge composting. The concentrations of the total Pb and the five Pb fractions concentrations were increased during the whole stage of compost. However, the percentages of Pb distribution with respect to total Pb were changed in the following manner: exchangeable, bound to Fe-Mn oxides and bound to carbonates Pb with respect to total Pb were increased, while the percentages of bound to organic matter and sulphides, and residual Pb with respect to total Pb were decreased during composting. The data showed that the quantity of Pb in the less toxic portion, such as consisting of organic matter and sulphides bound and residual Pb, was increased, and that the contamination and bio-availability of heavy metal Pb in sewage sludge was reduced during the composting process.

  13. Reviews on atmospheric selenium: Emissions, speciation and fate

    NASA Astrophysics Data System (ADS)

    Wen, Hanjie; Carignan, Jean

    The atmosphere is an important transient reservoir of selenium (Se). According to recent evaluations of the global Se budget, approximately 13,000-19,000 tons of Se is cycled through the troposphere annually. Most studies suggest that atmospheric deposition is an important source of Se contamination and it is therefore critical to evaluate the source emissions and fate of Se in the atmosphere. This paper presents a broad overview of current state of knowledge and understanding of major aspects of atmospheric Se and its natural and anthropogenic sources. The significant physical and chemical species encountered in the atmosphere are examined and special attention is paid to atmospheric speciation and its atmospheric pathways and processes. In addition, thermodynamic and kinetic data for atmospheric Se speciation are provided, which aid our understanding and the modelling of Se behaviour in the atmospheric environment. We also document how Se isotopes might be useful for tracing atmospheric sources and pathways. Important gaps in our current knowledge of Se in the atmospheric environment are identified, and suggestions for future research are offered.

  14. Astatine standard redox potentials and speciation in acidic medium.

    PubMed

    Champion, J; Alliot, C; Renault, E; Mokili, B M; Chérel, M; Galland, N; Montavon, G

    2010-01-14

    A combined experimental and theoretical approach is used to define astatine (At) speciation in acidic aqueous solution and to answer the two main questions raised from literature data: does At(0) exist in aqueous solution and what is the chemical form of At(+III), if it exists. The experimental approach considers that a given species is characterized by its distribution coefficient (D) experimentally determined in a biphasic system. The change in speciation arising from a change in experimental conditions is observed by a change in D value. The theoretical approach involves quasi-relativistic quantum chemistry calculations. The results show that At at the oxidation state 0 cannot exist in aqueous solution. The three oxidation states present in the range of water stability are At(-I), At(+I), and At(+III) and exist as At(-), At(+), and AtO(+), respectively, in the 1-2 pH range. The standard redox potentials of the At(+)/At(-) and AtO(+)/At(+) couples have been determined, the respective values being 0.36 +/- 0.01 and 0.74 +/- 0.01 V vs NHE. PMID:20014840

  15. Evaluation of mercury speciation by EPA (Draft) Method 29

    SciTech Connect

    Laudal, D.L.; Heidt, M.K.; Nott, B.

    1995-11-01

    The 1990 Clean Air Act Amendments require that the U.S. Environmental protection Agency (EPA) assess the health risks associated with mercury emissions. Also, the law requires a separate assessment of health risks posed by the emission of 189 tract chemicals (including mercury) for electric utility steam-generating units. In order to conduct a meaningful assessment of health and environmental effects, we must have, among other things, a reliable and accurate method to measure mercury emissions. In addition, the rate of mercury deposition and the type of control strategies used may depend upon the type of mercury emitted (i.e., whether it is in the oxidized or elemental form). It has been speculated that EPA (Draft) Method 29 can speciate mercury by selective absorption; however, this claim has yet to be proven. The Electric Power Research Institute (EPRI) and the U.S. Department of Energy (DOE) have contracted with the Energy & Environmental Research Center (EERC) at University of North Dakota to evaluate EPA (Draft) Method 29 at the pilot-scale level. The objective of the work is to determine whether EPA (Draft) Method 29 can reliably quantify and speciate mercury in the flue gas from coal-fired boilers.

  16. Astatine standard redox potentials and speciation in acidic medium.

    PubMed

    Champion, J; Alliot, C; Renault, E; Mokili, B M; Chérel, M; Galland, N; Montavon, G

    2010-01-14

    A combined experimental and theoretical approach is used to define astatine (At) speciation in acidic aqueous solution and to answer the two main questions raised from literature data: does At(0) exist in aqueous solution and what is the chemical form of At(+III), if it exists. The experimental approach considers that a given species is characterized by its distribution coefficient (D) experimentally determined in a biphasic system. The change in speciation arising from a change in experimental conditions is observed by a change in D value. The theoretical approach involves quasi-relativistic quantum chemistry calculations. The results show that At at the oxidation state 0 cannot exist in aqueous solution. The three oxidation states present in the range of water stability are At(-I), At(+I), and At(+III) and exist as At(-), At(+), and AtO(+), respectively, in the 1-2 pH range. The standard redox potentials of the At(+)/At(-) and AtO(+)/At(+) couples have been determined, the respective values being 0.36 +/- 0.01 and 0.74 +/- 0.01 V vs NHE.

  17. Analysis and stability of mercury speciation in petroleum hydrocarbons.

    PubMed

    Bloom, N S

    2000-03-01

    Raw petroleum and natural gas often contain high concentrations of mercury, which can be damaging to the metal components of production facilities, as well as to the environment. Various Hg species have different properties in terms of mobility, reactivity and bioavailability. Thus, for cost-effective decisions regarding plant design, Hg extraction, and pollution control, speciation information must be available at the production facility. In this paper, a simple, wet chemical speciation method, which provides data on Hg(o), dissolved and particulate total Hg, Hg(II), and methyl Hg is presented. The method incorporates species-specific extraction and separation procedures, followed by cold vapor atomic fluorescence spectrometry (CVAFS). For each species, detection limits of approximately 0.1 ng/g were obtained. Storage experiments in various containers showed that organo-mercury species were stable for at least 30 days in all containers except those made of polyethylene; and Hg(o) was stable in all containers except those made of stainless steel or polyethylene. Hg(II) was rapidly lost from all containers except those made of aluminum, which rapidly converted it to Hg(o), which was stable. In general, most of the total Hg in petroleum products was particulate Hg, followed by dissolved Hg(II) and Hg(o). Sub-ng/g concentrations of methyl-Hg were observed in most samples.

  18. 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...

  19. 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...

  20. Investigating Chemical and Thermodynamic Conditions that Determine the Aerosol Inorganic Nitrate Size Distribution: Insights from Speciated PM2.5 and PM10 Hourly Datasets from an Urban Site

    NASA Astrophysics Data System (ADS)

    Griffith, S. M.; Huang, X. H. H.; Louie, P. K. K.; Yu, J. Z.

    2015-12-01

    Nitric acid (HNO3), the gas-phase precursor to aerosol nitrate is known to rapidly transfer to aerosols where NH4+ is in excess to SO42- present in the aerosol, but the HNO3 is also subject to the slower uptake onto sea salt and dust laden particles. Understanding the competition between these routes is necessary to predict the NO3- distribution and impact on aerosols. In this study, we investigated the conditions leading to predominant fine or coarse mode aerosol nitrate using an hourly MARGA 2S dataset from an urban site in Hong Kong. The hourly dataset of inorganic ions (SO42-, NH4+, NO3-, Na+, Cl-, Ca2+, K+, Mg2+) in 2 size ranges (fine, < 2.5 μm; fine+coarse, < 10 μm) and water-soluble gases (HNO3, HCl, and NH3) spanning more than 1 year provides a rich trove for analyzing aerosol nitrate chemistry and the underlying mechanisms that ultimately determine the fraction of NO3- in the fine mode. The urban site in this study is initially characterized for seasonal environmental conditions and the aerosol chemical composition. The relationship between excess NH4+ and NO3- in the fine mode is detailed and contrasted with the influence on fine mode NO3- from uptake on sea salt and dust, which is typically relegated as a 'coarse-mode' mechanism. The distribution of NO3- in the fine and coarse modes is compared with the distribution of the other inorganic ions, where sea-salt ion (Na+, Mg2+) distributions yield the highest explained variability for the nitrate distributions. As a complement to that finding, the cation equivalency (excluding NH4+) in the coarse mode proves to be a crucial factor in leveraging the distribution away from fine mode nitrate. The uptake potential of the water-soluble gases is used to drive a mass transfer model and compare with thermodynamic equilibrium results. In the modeling, the partitioning cycles of fine and coarse mode aerosol nitrate highlight the dynamic relationship between NO3- and Cl- in both the fine and coarse modes, where the

  1. Instrumentation for Aerosol and Gas Speciation

    NASA Technical Reports Server (NTRS)

    Coggiola, Michael J.

    1998-01-01

    Using support from NASA Grant No. NAG 2-963, SRI International successfully completed the project, entitled, 'Instrumentation for Aerosol and Gas Speciation.' This effort (SRI Project 7383) covered the design, fabrication, testing, and deployment of a real-time aerosol speciation instrument in NASA's DC-8 aircraft during the Spring 1996 SUbsonic aircraft: Contrail and Cloud Effects Special Study (SUCCESS) mission. This final technical report describes the pertinent details of the instrument design, its abilities, its deployment during SUCCESS and the data acquired from the mission, and the post-mission calibration, data reduction, and analysis.

  2. Phenotypic plasticity's impacts on diversification and speciation.

    PubMed

    Pfennig, David W; Wund, Matthew A; Snell-Rood, Emilie C; Cruickshank, Tami; Schlichting, Carl D; Moczek, Armin P

    2010-08-01

    Phenotypic plasticity (the ability of a single genotype to produce multiple phenotypes in response to variation in the environment) is commonplace. Yet its evolutionary significance remains controversial, especially in regard to whether and how it impacts diversification and speciation. Here, we review recent theory on how plasticity promotes: (i) the origin of novel phenotypes, (ii) divergence among populations and species, (iii) the formation of new species and (iv) adaptive radiation. We also discuss the latest empirical support for each of these evolutionary pathways to diversification and identify potentially profitable areas for future research. Generally, phenotypic plasticity can play a largely underappreciated role in driving diversification and speciation.

  3. Arsenic speciation in manufactured seafood products.

    PubMed

    Vélez, D; Montoro, R

    1998-09-01

    The literature on the speciation of arsenic (As) in seafoods was critically reviewed. Most research has been directed toward fresh seafood products with few papers dealing with As speciation in manufactured seafoods. Predictions concerning As species made on the basis of fresh seafood products cannot be extrapolated to manufactured seafoods. Therefore, due to the numerous species of As, the scarcity of data concerning their presence in foods, the transformations each species may undergo during industrial processing and cooking, and the lack of legislation on permitted As levels in seafood products, As species in manufactured seafood products need to be determined and quantified.

  4. Phosphorous Speciation in WTR-treated Biosolids Using XANES

    NASA Astrophysics Data System (ADS)

    Zhang, T. Q.; Huff, D.; Lin, Z.-Q.

    2009-04-01

    The concept of co-application of biosolids and drinking water treatment residues (DWTRs) represents an environmentally sustainable and economically sound strategy for the management of municipal solid wastes. This study demonstrated the effectiveness of reducing water-soluble P in biosolids-amended agricultural soil by the addition of DWTRs. Results showed that total P in soil leachate was significantly reduced during the initial 42-days of a 200-day greenhouse study when biosolids (50 g kg-1) were applied along with DWTRs (40 g kg-1). Particulate P was the dominant fraction of P in the soil leachate, which decreases with increasing DWTR application rate. The application of DWTRs does not significantly decrease the growth and yield of wheat (Triticum aestivum L.). The primary P chemical composition in biosolids include cupper phytate [Cu(IP6)6], barium phytate [Ba6IP6], and cupper phosphate [Cu3(PO4)2]. The addition of DWTRs to biosolids alternated the P speciation, and the P speciation change became significant with increasing the incubation time of the mixture of biosolids and DWTRs. The chemical component of Cu3(PO4)2 became non significant (<5%) with the addition of DWTRs. During the 14-day incubation time period, the proportion of P that was adsorbed on amorphous Fe(OH)3 increased substantially from 8 to 46% and Ba6IP6 increased steadily from 30 to 50%, while the proportion of Cu(IP6)6 decreased significantly from 53 to 5%. The amorphous Fe(OH)3-adsorbed P and Ba6IP6 formed the dominant P chemical components in the mixture of biosolids and DWTRs.

  5. Speciation: Genomic Archipelagos in a Crater Lake.

    PubMed

    Ronco, Fabrizia; Salzburger, Walter

    2016-03-01

    The opening stages of speciation remain poorly understood, especially from a genomic perspective. The genomes of newly discovered crater-lake cichlid fish shed light on the early phases of diversification and suggest that selection acts on multiple genomic regions. PMID:26954438

  6. Speciation of VOCs from Animal Feeding Operations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Environmental Pollution Agency (EPA) air consent agreement with animal feeding operations (AFO) specifies the use of EPA TO-15 for the speciation of volatile organic compounds (VOC) emitted from these facilities. However, compounds emitted from AFO are often both volatile and highly polar chara...

  7. Ecological speciation in tropical reef fishes.

    PubMed

    Rocha, Luiz A; Robertson, D Ross; Roman, Joe; Bowen, Brian W

    2005-03-22

    The high biodiversity in tropical seas provides a long-standing challenge to allopatric speciation models. Physical barriers are few in the ocean and larval dispersal is often extensive, a combination that should reduce opportunities for speciation. Yet coral reefs are among the most species-rich habitats in the world, indicating evolutionary processes beyond conventional allopatry. In a survey of mtDNA sequences of five congeneric west Atlantic reef fishes (wrasses, genus Halichoeres) with similar dispersal potential, we observed phylogeographical patterns that contradict expectations of geographical isolation, and instead indicate a role for ecological speciation. In Halichoeres bivittatus and the species pair Halichoeres radiatus/brasiliensis, we observed strong partitions (3.4% and 2.3% divergence, respectively) between adjacent and ecologically distinct habitats, but high genetic connectivity between similar habitats separated by thousands of kilometres. This habitat partitioning is maintained even at a local scale where H. bivittatus lineages are segregated between cold- and warm-water habitats in both Bermuda and Florida. The concordance of evolutionary partitions with habitat types, rather than conventional biogeographical barriers, indicates parapatric ecological speciation, in which adaptation to alternative environmental conditions in adjacent locations overwhelms the homogenizing effect of dispersal. This mechanism can explain the long-standing enigma of high biodiversity in coral reef faunas.

  8. Characterization of Technetium Speciation in Cast Stone

    SciTech Connect

    Um, Wooyong; Jung, Hun Bok; Wang, Guohui; Westsik, Joseph H.; Peterson, Reid A.

    2013-11-11

    This report describes the results from laboratory tests performed at Pacific Northwest National Laboratory (PNNL) for the U.S. Department of Energy (DOE) EM-31 Support Program (EMSP) subtask, “Production and Long-Term Performance of Low Temperature Waste Forms” to provide additional information on technetium (Tc) speciation characterization in the Cast Stone waste form. To support the use of Cast Stone as an alternative to vitrification for solidifying low-activity waste (LAW) and as the current baseline waste form for secondary waste streams at the Hanford Site, additional understanding of Tc speciation in Cast Stone is needed to predict the long-term Tc leachability from Cast Stone and to meet the regulatory disposal-facility performance requirements for the Integrated Disposal Facility (IDF). Characterizations of the Tc speciation within the Cast Stone after leaching under various conditions provide insights into how the Tc is retained and released. The data generated by the laboratory tests described in this report provide both empirical and more scientific information to increase our understanding of Tc speciation in Cast Stone and its release mechanism under relevant leaching processes for the purpose of filling data gaps and to support the long-term risk and performance assessments of Cast Stone in the IDF at the Hanford Site.

  9. ARSENIC SPECIATION ANALYSIS IN HUMAN SALIVA

    EPA Science Inventory

    Background: Determination of arsenic species in human saliva is potentially useful for biomonitoring of human exposure to arsenic and for studying arsenic metabolism. However, there is no report on the speciation analysis of arsenic in saliva. Methods: Arsenic species in saliva ...

  10. Sympatric speciation by allochrony in a seabird.

    PubMed

    Friesen, V L; Smith, A L; Gómez-Díaz, E; Bolton, M; Furness, R W; González-Solís, J; Monteiro, L R

    2007-11-20

    The importance of sympatric speciation (the evolution of reproductive isolation between codistributed populations) in generating biodiversity is highly controversial. Whereas potential examples of sympatric speciation exist for plants, insects, and fishes, most theoretical models suggest that it requires conditions that are probably not common in nature, and only two possible cases have been described for tetrapods. One mechanism by which it could occur is through allochronic isolation-separation of populations by breeding time. Oceanodroma castro (the Madeiran or band-rumped storm-petrel) is a small seabird that nests on tropical and subtropical islands throughout the Atlantic and Pacific Oceans. In at least five archipelagos, different individuals breed on the same islands in different seasons. We compared variation in five microsatellite loci and the mitochondrial control region among 562 O. castro from throughout the species' range. We found that sympatric seasonal populations differ genetically within all five archipelagos and have ceased to exchange genes in two. Population and gene trees all indicate that seasonal populations within four of the archipelagos are more closely related to each other than to populations from the same season from other archipelagos; divergence of the fifth sympatric pair is too ancient for reliable inference. Thus, seasonal populations appear to have arisen sympatrically at least four times. This is the first evidence for sympatric speciation by allochrony in a tetrapod, and adds to growing indications that population differentiation and speciation can occur without geographic barriers to gene flow. PMID:18006662

  11. Actinide speciation in relation to biological processes.

    PubMed

    Ansoborlo, Eric; Prat, Odette; Moisy, Philippe; Den Auwer, Christophe; Guilbaud, Philippe; Carriere, M; Gouget, Barbara; Duffield, John; Doizi, Denis; Vercouter, Thomas; Moulin, Christophe; Moulin, Valérie

    2006-11-01

    In case of accidental release of radionuclides into the environment, actinides represent a severe health risk to human beings following internal contamination (inhalation, ingestion or wound). For a better understanding of the actinide behaviour in man (in term of metabolism, retention, excretion) and in specific biological systems (organs, cells or biochemical pathways), it is of prime importance to have a good knowledge of the relevant actinide solution chemistry and biochemistry, in particular of the thermodynamic constants needed for computing actinide speciation. To a large extent, speciation governs bioavailability and toxicity of elements and has a significant impact on the mechanisms by which toxics accumulate in cell compartments and organs and by which elements are transferred and transported from cell to cell. From another viewpoint, speciation is the prerequisite for the design and success of potential decorporation therapies. The purpose of this review is to present the state of the art of actinide knowledge within biological media. It is also to discuss how actinide speciation can be determined or predicted and to highlight the areas where information is lacking with the aim to encourage new research efforts.

  12. EFFECT OF SCR CATALYST ON MERCURY SPECIATION

    EPA Science Inventory

    A pilot-scale research study was conducted to investigate the effect of selective catalytic reduction (SCR) on elemental mercury speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois bituminous coals and one Powder River Basin (PRB) coal...

  13. Biosensor for metal analysis and speciation

    DOEpatents

    Aiken, Abigail M.; Peyton, Brent M.; Apel, William A.; Petersen, James N.

    2007-01-30

    A biosensor for metal analysis and speciation is disclosed. The biosensor comprises an electron carrier immobilized to a surface of an electrode and a layer of an immobilized enzyme adjacent to the electrode. The immobilized enzyme comprises an enzyme having biological activity inhibited by a metal to be detected by the biosensor.

  14. Chromosome speciation: Humans, Drosophila, and mosquitoes

    PubMed Central

    Ayala, Francisco J.; Coluzzi, Mario

    2005-01-01

    Chromosome rearrangements (such as inversions, fusions, and fissions) may play significant roles in the speciation between parapatric (contiguous) or partly sympatric (geographically overlapping) populations. According to the “hybrid-dysfunction” model, speciation occurs because hybrids with heterozygous chromosome rearrangements produce dysfunctional gametes and thus have low reproductive fitness. Natural selection will, therefore, promote mutations that reduce the probability of intercrossing between populations carrying different rearrangements and thus promote their reproductive isolation. This model encounters a disabling difficulty: namely, how to account for the spread in a population of a chromosome rearrangement after it first arises as a mutation in a single individual. The “suppressed-recombination” model of speciation points out that chromosome rearrangements act as a genetic filter between populations. Mutations associated with the rearranged chromosomes cannot flow from one to another population, whereas genetic exchange will freely occur between colinear chromosomes. Mutations adaptive to local conditions will, therefore, accumulate differentially in the protected chromosome regions so that parapatric or partially sympatric populations will genetically differentiate, eventually evolving into different species. The speciation model of suppressed recombination has recently been tested by gene and DNA sequence comparisons between humans and chimpanzees, between Drosophila species, and between species related to Anopheles gambiae, the vector of malignant malaria in Africa. PMID:15851677

  15. Overview of receptor-based source apportionment studies for speciated atmospheric mercury

    NASA Astrophysics Data System (ADS)

    Cheng, I.; Xu, X.; Zhang, L.

    2015-07-01

    Receptor-based source apportionment studies of speciated atmospheric mercury are not only concerned with source contributions but also with the influence of transport, transformation, and deposition processes on speciated atmospheric mercury concentrations at receptor locations. Previous studies applied multivariate receptor models including principal components analysis and positive matrix factorization, and back trajectory receptor models including potential source contribution function, gridded frequency distributions, and concentration-back trajectory models. Combustion sources (e.g., coal combustion, biomass burning, and vehicular, industrial and waste incineration emissions), crustal/soil dust, and chemical and physical processes, such as gaseous elemental mercury (GEM) oxidation reactions, boundary layer mixing, and GEM flux from surfaces were inferred from the multivariate studies, which were predominantly conducted at receptor sites in Canada and the US. Back trajectory receptor models revealed potential impacts of large industrial areas such as the Ohio River valley in the US and throughout China, metal smelters, mercury evasion from the ocean and the Great Lakes, and free troposphere transport on receptor measurements. Input data and model parameters specific to atmospheric mercury receptor models are summarized and model strengths and weaknesses are also discussed. Multivariate models are suitable for receptor locations with intensive air monitoring because they require long-term collocated and simultaneous measurements of speciated atmospheric Hg and ancillary pollutants. The multivariate models provide more insight about the types of Hg emission sources and Hg processes that could affect speciated atmospheric Hg at a receptor location, whereas back trajectory receptor models are mainly ideal for identifying potential regional Hg source locations impacting elevated Hg concentrations. Interpretation of the multivariate model output to sources can be

  16. Comparing Modeled and Measured Mercury Speciation in Contaminated Groundwater: Importance of Dissolved Organic Matter Composition.

    PubMed

    Richard, Jan-Helge; Bischoff, Cornelia; Biester, Harald

    2016-07-19

    In addition to analytical speciation, reliable Hg species modeling is crucial for predicting the mobility and toxicity of Hg, but geochemical speciation codes have not yet been tested for their prediction accuracy. Our study compares analyses of Hg species in highly Hg-contaminated groundwater (Hgtot: 0.02-4 μmol·L(-1)) at three sites with predictions of Hg speciation obtained from three geochemical codes (WHAM, Visual MINTEQ, PHREEQC) with and without implementation of Hg complexation by dissolved organic matter (DOM). Samples were analyzed for chemical composition, elemental, inorganic, and DOM-bound Hg (Hg(0), Hginorg, HgDOM). Hg-DOM complexation was modeled using three approaches: binding to humic/fulvic acids, binding to thiol-groups, or a combination of both. Results of Hg(0) modeling were poor in all scenarios. Prediction accuracy for Hginorg and HgDOM strongly depended on the assumed DOM composition. Best results were achieved when weaker binding sites, simulated by WHAMs DOM submodel, were combined with strongly binding thiol groups. Indications were found that thiol-DOM ratios in groundwater are likely to be lower than in surface water, highlighting the need for analytical thiol quantification in groundwater DOM. This study shows that DOM quality is a crucial parameter for prediction of Hg speciation in groundwater by means of geochemical modeling. PMID:27328766

  17. Aerosol speciation and mass prediction from toluene oxidation under high NO x conditions

    NASA Astrophysics Data System (ADS)

    Kelly, Janya L.; Michelangeli, Diane V.; Makar, Paul A.; Hastie, Donald R.; Mozurkewich, Michael; Auld, Janeen

    2010-01-01

    A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO x conditions (VOC/NO x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m -3 (range of 5-145 μg m -3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73-88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO x conditions. Further research into the yields and speciation leading to this reaction product is recommended.

  18. Mathematical modeling of the effects of aerobic and anaerobic chelate bioegradation on actinide speciation.

    SciTech Connect

    Banaszak, J.E.; VanBriesen, J.; Rittmann, B.E.; Reed, D.T.

    1998-03-19

    Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and, hence, the mobility of actinides in subsurface environments. We combined mathematical modeling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bio-utilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCBATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modeling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems.

  19. Speciation of Energetic Materials on a Microcantilever Using Surface Reduction

    SciTech Connect

    Yi, Dechang; Senesac, Larry R; Thundat, Thomas George

    2008-01-01

    Although microcantilevers have been used to detect explosives with extremely high sensitivity using variations in adsorption-induced bending and resonance frequency, obtaining selectivity remains a challenge. Reversible chemoselectivity at ambient temperatures based on receptor-based detection provides only limited selectivity due to the generality of chemical interactions. The oxygen imbalance in secondary explosives presents a means to achieve receptor-free speciation of explosives using surface reduction of adsorbed molecules. We demonstrate highly selective and real-time detection of Trinitrotoluene (TNT) using a copper oxide-coated cantilever with a surface reduction approach. Not only can this technique exclusively differentiate explosives from nonexplosives, but also it has the potential to specify individual explosives such as TNT, pentaerythritol tetranitrate (PETN), and RDX. This technique together with receptor-based detection techniques provides a multimodal approach for achieving very high selectivity.

  20. Plutonium, americium, and neptunium speciation in selected groundwaters

    USGS Publications Warehouse

    Cleveland, J.M.; Rees, T.F.; Nash, K.L.

    1985-01-01

    Speciation was determined at 25 and 90 degree C in four groundwaters from diverse sources: the Sparta aquifer in Louisiana, near the Vacherie salt dome; Mansfield No. 2 well in the Palo Duro Basin, Texas; the Stripa mine in Sweden; and the Waste Isolation Pilot Plant in New Mexico. Neptunium generally was soluble in all waters and was present exclusively as Np(V) and Np(VI), regardless of initial oxidation state. The results indicated that plutonium and neptunium solubilities were determined by the oxidation-reduction properties of the waters, i. e. , their abilities to convert these elements to soluble oxidation states. This was not the case for americium, however; Am(IV) was not detected, and the solubility of this element was determined entirely by the chemical properties of Am(III).

  1. Actinide solubility and spectroscopic speciation in alkaline Hanford waste solutions

    SciTech Connect

    Rao, L.; Felmy, A.R.; Rai, D.

    1996-10-01

    Information on the solubility and the speciation of actinide elements, especially plutonium and neptunium, in alkaline solutions is of importance in the development of separation techniques for the Hanford tank HLW supernatant. In the present study, experimental data on the solubilities of plutonium in simulated Hanford tank solutions were analyzed with Pitzer`s specific ion-interaction approach, which is applicable in dilute to highly concentrated electrolyte solutions. In order to investigate the formation of actinide species in alkaline solutions with ligands (e.g., hydroxide, aluminate and carbonate), spectroscopic measurements of neptunium (V), as a chemical analog of plutonium (V), were conducted. Based on the solubility data and available information on both solid and aqueous species, a thermodynamic model was proposed. The applicability and limitations of this model are discussed.

  2. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur

    EPA Science Inventory

    In North America, the dry component of total nitrogen and sulfur deposition remains uncertain due to a lack of measurements of sufficient chemical speciation and temporal extent to develop complete annual mass budgets or of sufficient process level detail to improve current air-s...

  3. Arsenic Speciation in Geothermal Waters

    NASA Astrophysics Data System (ADS)

    Keller, N. S.; Stefansson, A.; Sigfusson, B.

    2011-12-01

    Various arsenic species have been observed or inferred in geothermal waters in recent years, in particular thio- and oxyanions. However their exact stoechiometry and their oxidation state has been subjected to a sustained debate over the last decade. Most of the As species seen in geothermal waters are unstable under laboratory conditions, thus it is crucial that appropriate sampling and analytical techniques are used in order to minimise post-sampling changes. The goals of this study were to determine how many As species can be seen in geothermal systems and how geochemical parameters control the number and relative abundance of the species. Furthermore, we tested the stability of the As-S compounds after sampling, in particular whether the traditionally used flash-freezing method quantitatively preserves the species. Samples were collected from wells at the Hellisheidi Power Plant and from natural hot springs in the Geysir Geothermal Area in SW Iceland. The samples were analysed on-site immediately after sampling by first separating the various As species by Ion Chromatography followed by quantification by Hydride-Generation Atomic Fluorescence Spectrometer (HG-AFS). Preliminary results show that analysis of the samples immediately after sampling is crucial, as sample storage and flash-freezing/thawing appear to modify the As speciation. Using the retention times of the analytes through the chromatographic column, a minimum of seven As species were observed. Two of the species are oxides of AsIII and AsV, based on the comparison of their retention times with standards. The other five species have yet to be unequivocally identified, but based on prior studies it is assumed that at least some of them are thioarsenic species with various S:O ratios, with longer retention times for increasing S:O. Clear differences can be seen between samples from Hellisheidi and Geysir. In the case of the oxyanions, only AsIII is present at Hellisheidi whereas both oxidation states

  4. Chemical Speciation of Inorganic Compounds under Hydrothermal Conditions

    SciTech Connect

    Edward A Stern; John Fulton

    2002-02-21

    Measurements of oxidation. These spectra are to the best of our knowledge the first reported in situ spectroscopic observation of homogeneous aqueous redox chemistry at temperatures beyond the critical temperature of waste. We also observed a time-dependence for the growth of the Cr(VI) XANES peak and have therefore obtained both kinetic information as well as structural information on the reactants and products at the reaction temperature. We feel that these new techniques, when employed on actual waste components will elucidate the underlying chemistry.

  5. Chemical speciation and adsorption behavior of plutonium in natural waters

    SciTech Connect

    Sanchez, A.L.

    1983-01-01

    Dissolved Pu profiles in two partially anoxic basins--Saanich Inlet, an intermittently anoxic marine fiord in Vancouver Island, British Columbia, and Soap Lake, a saline, alkaline lake in eastern Washington state, revealed minimum concentrations at the O/sub 2//H/sub 2/S interface. The Pu concentrations in the anoxic waters of Saanich Inlet were less than the surface concentrations; however, in Soap Lake, a 15- to 50-fold increase in Pu concentration in the anoxic monimolimnion correlated with large increases in the major ions, total alkalinity, and dissolved organic carbon. Laboratory experiments were designed to investigate the effects of pH, ionic strength, dissolved organic carbon, and carbonate ions on the adsorption of tracer amounts of Pu IV and Pu V. The Pu-goethite adsorption system provided the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. Pu IV and Pu V interacted very differently with goethite, which is consistent with their different hydrolytic character. A reduction of Pu V to Pu IV occurred on the goethite surface and also on montmorillonite and silica gel, suggesting that redox transformations are an important aspect of Pu adsorption. Increases in ionic strength (up to 3 M NaCl or NaNO/sub 3/) did not affect Pu IV or V adsorption. In the presence of dissolved organic carbon (DOC), Pu V reduction to Pu IV occurred in solution. Pu IV adsorption on goethite decreased only 30% in the presence of 240 ppm of natural DOC from Soap Lake; however, carbonate anions inhibited Pu IV adsorption on goethite at the alkalinity levels (1500 meq/L total alkalinity, 0.57 M CO/sub 3/=) measured for Soap Lake monimolimnion waters.

  6. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Kim, C.S.; Brown, Gordon E.; Rytuba, J.J.

    2000-01-01

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis

  7. Comparisons of Speciated PM-2.5 Mass at Rural and Urban New York State Locations

    NASA Astrophysics Data System (ADS)

    Felton, H.; Civerolo, K.; Schwab, J. J.; Demerjian, K. L.

    2002-12-01

    The EPA Speciation Monitoring program is designed to determine the concentrations of 58 compounds contributing to the composition of ambient atmospheric particles smaller than 2.5 microns at various locations. Typically, siting criteria favor areas representative of high population exposure and relatively strong local pollution sources. The New York State Department of Environmental Conservation; (NYSDEC) in conjunction with the New York PMTACS Supersite program has augmented the predominantly urban PM-2.5 speciation network with measurements at two rural monitoring sites. In addition to providing data well suited to characterizing the composition of regional PM-2.5 air quality these sites provide the opportunity to compare filter based speciation data to measurements performed with the newest continuous speciation instrumentation technologies. PM-2.5 chemical speciation samplers draw from 600 to 1000 liters of air per hour across three filters simultaneously over a 24 hour period. The three filters are subjected to specific lab analyses to determine the concentrations of targeted compounds; including metals, ions such as sulfate, nitrate, and ammonium, and elemental and organic carbon. Data from these sites are collected on a one day in three schedule and are available for a year or more from the various locations. PM-2.5 speciation data are used to determine a ranking of compounds responsible for particulate pollution in various geographical locations in New York State. This information is useful in the attribution of sources to observed PM-2.5 concentrations and in the identification of the differences and similarities of these contributions in urban versus rural environments. PM-2.5 speciation data were obtained at two rural locations, Pinnacle State Park near Corning, NY and Whiteface Mountain in the Adirondacks; and at two urban locations, Rochester, NY and New York City, NY. Comparisons of the rural and urban measurement data suggest that compounds such as

  8. Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

    PubMed Central

    Jabłońska-Czapla, Magdalena

    2015-01-01

    Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

  9. The Genetics of Speciation by Reinforcement

    PubMed Central

    2004-01-01

    Reinforcement occurs when natural selection strengthens behavioral discrimination to prevent costly interspecies matings, such as when matings produce sterile hybrids. This evolutionary process can complete speciation, thereby providing a direct link between Darwin's theory of natural selection and the origin of new species. Here, by examining a case of speciation by reinforcement in Drosophila, we present the first high-resolution genetic study of variation within species for female mating discrimination that is enhanced by natural selection. We show that reinforced mating discrimination is inherited as a dominant trait, exhibits variability within species, and may be influenced by a known set of candidate genes involved in olfaction. Our results show that the genetics of reinforced mating discrimination is different from the genetics of mating discrimination between species, suggesting that overall mating discrimination might be a composite phenomenon, which in Drosophila could involve both auditory and olfactory cues. Examining the genetics of reinforcement provides a unique opportunity for both understanding the origin of new species in the face of gene flow and identifying the genetic basis of adaptive female species preferences, two major gaps in our understanding of speciation. PMID:15550988

  10. First passage time to allopatric speciation

    PubMed Central

    Yamaguchi, Ryo; Iwasa, Yoh

    2013-01-01

    Allopatric speciation is a mechanism to evolve reproductive isolation; it is caused by the accumulation of genetic differences between populations while they are geographically isolated. Here, we studied a simple stochastic model for the time until speciation caused by geographical isolation in fragmented populations that experience recurrent but infrequent migration between subpopulations. We assumed that mating incompatibility is controlled by a number of loci that behave as neutral characters in the accumulation of novel mutations within each population. Genetic distance between populations was defined as the number of incompatibility-controlling loci that differ between them. Genetic distance increases through the separate accumulation of mutations in different populations, but decreases after a successful migration event followed by genetic mixing between migrants and residents. We calculated the time to allopatric speciation, which occurs when the genetic distance exceeds a specified threshold. If the number of invasive individuals relative to the resident population is not very large, diffusion approximation provides an accurate prediction. There is an intermediate optimal rate of migration that maximizes the rate of species creation by recurrent invasion and diversification. We also examined cases that involved more than two populations. PMID:24516714

  11. The genetics of speciation by reinforcement.

    PubMed

    Ortiz-Barrientos, Daniel; Counterman, Brian A; Noor, Mohamed A F

    2004-12-01

    Reinforcement occurs when natural selection strengthens behavioral discrimination to prevent costly interspecies matings, such as when matings produce sterile hybrids. This evolutionary process can complete speciation, thereby providing a direct link between Darwin's theory of natural selection and the origin of new species. Here, by examining a case of speciation by reinforcement in Drosophila,we present the first high-resolution genetic study of variation within species for female mating discrimination that is enhanced by natural selection. We show that reinforced mating discrimination is inherited as a dominant trait, exhibits variability within species, and may be influenced by a known set of candidate genes involved in olfaction. Our results show that the genetics of reinforced mating discrimination is different from the genetics of mating discrimination between species, suggesting that overall mating discrimination might be a composite phenomenon, which in Drosophila could involve both auditory and olfactory cues. Examining the genetics of reinforcement provides a unique opportunity for both understanding the origin of new species in the face of gene flow and identifying the genetic basis of adaptive female species preferences, two major gaps in our understanding of speciation.

  12. Determination of metal speciation by reverse titrations.

    PubMed

    Nuester, Jochen; van den Berg, Constant M G

    2005-01-01

    A new method is proposed to determine metal speciation by varying the concentration of a competing ligand at a constant metal concentration, with detection by cathodic stripping voltammetry. The free metal ion concentration is gradually lowered from its natural level while the method probes progressively deeper into the already complexed metal fraction: it is therefore a reverse titration rather than the forward titration which is used for conventional complexing ligand titrations. The sensitivity is greatest at the lowest free metal ion concentration, where it matters most, and the method can be carried out in a single sample aliquot in the voltammetric cell. The method is applied here to copper speciation, but in principle, it can also be used for other metals. Modeling shows that this method has good sensitivity at ligand concentrations near the metal concentration (lower as well as greater). Comparative measurements of copper speciation using reverse and forward titrations of representative water samples of oceanic and coastal origin show good agreement. The data showed that these samples did not contain low levels of strong ligands in addition to the ligands detected by the forward titrations.

  13. Floral symmetry affects speciation rates in angiosperms.

    PubMed Central

    Sargent, Risa D.

    2004-01-01

    Despite much recent activity in the field of pollination biology, the extent to which animal pollinators drive the formation of new angiosperm species remains unresolved. One problem has been identifying floral adaptations that promote reproductive isolation. The evolution of a bilaterally symmetrical corolla restricts the direction of approach and movement of pollinators on and between flowers. Restricting pollinators to approaching a flower from a single direction facilitates specific placement of pollen on the pollinator. When coupled with pollinator constancy, precise pollen placement can increase the probability that pollen grains reach a compatible stigma. This has the potential to generate reproductive isolation between species, because mutations that cause changes in the placement of pollen on the pollinator may decrease gene flow between incipient species. I predict that animal-pollinated lineages that possess bilaterally symmetrical flowers should have higher speciation rates than lineages possessing radially symmetrical flowers. Using sister-group comparisons I demonstrate that bilaterally symmetric lineages tend to be more species rich than their radially symmetrical sister lineages. This study supports an important role for pollinator-mediated speciation and demonstrates that floral morphology plays a key role in angiosperm speciation. PMID:15156918

  14. Interactions among quantitative traits in the course of sympatric speciation

    NASA Astrophysics Data System (ADS)

    Kondrashov, Alexey S.; Kondrashov, Fyodor A.

    1999-07-01

    Sympatric speciation, the origin of two or more species from a single local population, has almost certainly been involved in formation of several species flocks, and may be fairly common in nature. The most straightforward scenario for sympatric speciation requires disruptive selection favouring two substantially different phenotypes, and consists of the evolution of reproductive isolation between them followed by the elimination of all intermediate phenotypes. Here we use the hypergeometric phenotypic model to show that sympatric speciation is possible even when fitness and mate choice depend on different quantitative traits, so that speciation must involve formation of covariance between these traits. The increase in the number of variable lociaffecting fitness facilitates sympatric speciation, whereas the increase in the number of variable loci affecting mate choice has the opposite effect. These predictions may enable more cases of sympatric speciation to be identified.

  15. Validating riverine transport and speciation models using nuclear reactor-derived radiocobalt.

    PubMed

    Albrecht, Achim

    2003-01-01

    Risk assessment of intentional or accidental discharges of toxic substances into river systems requires combined hydraulic and chemical modeling. Periodic discharges of known volumes with low radioactivity by the Beznau nuclear reactor (Switzerland) serve as validation tracers for both river flow and chemical speciation simulation. Validation of the former has been achieved by comparison of modeled and measured arrival times of radiocobalt along a 65 km transect with a maximum reaction period of 24 hours. Modeled breakthrough curves coincide well with measurements collected during three field campaigns, in spite of the fact that sorption and sedimentation processes were not activated during simulation. This gives indirect evidence of inefficient cobalt sorption. Particle/solution distribution measurements carried out during breakthrough allow further validation of our speciation approach, which is based on Tableau setup of inorganic reactions combined with sorption and organic complexation. Modeled and measured speciation results confirm recent observations of enhanced complexation of cobalt with dissolved organic substances, which significantly reduces particle sorption. The large variability of conditional stability constants for sorption and complexation reactions, for sorption site densities, and for organic ligand concentrations explains the variability of published particle-solution distribution coefficients.

  16. Speciation-dependent toxicity of neptunium(V) toward chelatobacter heintzii.

    SciTech Connect

    Banaszak, J. E.; Reed, D. T.; Rittmann, B. E.; Chemical Engineering; Northwestern Univ.

    1998-04-15

    This work investigates how chemical speciation controls the toxicity of neptunium and the neptunium-NTA complex toward Chelatobacter heintzii. We studied the effect of aquo and complexed/precipitated neptunium on the growth of C. heintzii in noncomplexing glucose and phosphate-buffered nitrilotriacetic acid (NTA) growth media. Equilibrium chemical speciation modeling and absorption spectroscopy were used to link neptunium speciation to biological growth inhibition. Our results show that metal toxicity of aquo NpO{sub 2}{sup +} significantly limits the growth of C. heintzii at free metal ion concentrations greater than {approx}10{sup -5} M. However, neptunium concentrations {ge}10{sup -4} M do not cause measurable radiotoxicity effects in C. heintzii when present in the form of a neptunium-NTA complex or colloidal/precipitated neptunium phosphate. The neptunium-NTA complex, which is stable under aerobic conditions, is destabilized by microbial degradation of NTA. When phosphate was present, degradation of NTA led to the precipitation of a neptunium-phosphate phase.

  17. Overview of receptor-based source apportionment studies for speciated atmospheric mercury

    NASA Astrophysics Data System (ADS)

    Cheng, I.; Xu, X.; Zhang, L.

    2015-02-01

    Receptor-based source apportionment studies of speciated atmospheric mercury are not only concerned with source contributions, but also the influence of transport, transformation, and deposition processes on speciated atmospheric mercury concentrations at receptor locations. Previous studies applied multivariate receptor models including Principal Components Analysis and Positive Matrix Factorization, and back trajectory receptor models including Potential Source Contribution Function, Gridded Frequency Distributions, and Concentration-back trajectory models. Anthropogenic combustion sources, crustal/soil dust, and chemical and physical processes, such as gaseous elemental mercury (GEM) oxidation reactions, boundary layer mixing, and GEM flux from surfaces, were inferred from the multivariate studies, which were predominantly conducted at receptor sites in Canada and the US. Back trajectory receptor models revealed potential impacts of large industrial areas such as the Ohio River Valley in the US and throughout China, metal smelters, mercury evasion from the ocean and Great Lakes, and free troposphere transport on receptor measurements. Input data and model parameters specific to atmospheric mercury receptor models are summarized and model strengths and weaknesses are also discussed. One area of improvement that applies to all receptor models is the greater focus on evaluating the accuracy of receptor models at identifying potential speciated atmospheric mercury sources, source locations, and chemical and physical processes in the atmosphere.

  18. Speciation of volatile organic compounds from poultry production

    NASA Astrophysics Data System (ADS)

    Trabue, Steven; Scoggin, Kenwood; Li, Hong; Burns, Robert; Xin, Hongwei; Hatfield, Jerry

    2010-09-01

    Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. The top five compounds made up close to 70% of VOCs and included: 1) acetic acid (830.1 μg m -3); 2) 2,3-butanedione (680.6 μg m -3); 3) methanol (195.8 μg m -3); 4) acetone (104.6 μg m -3); and 5) ethanol (101.9 μg m -3). Location variations for top five compounds averaged 49.5% in each section of the building and averaged 87% for the entire building.

  19. Field Deployable Method for Arsenic Speciation in Water

    PubMed Central

    Voice, Thomas C.; Flores del Pino, Lisveth V.; Havezov, Ivan; Long, David T.

    2010-01-01

    Contamination of drinking water supplies by arsenic is a world-wide problem. Total arsenic measurements are commonly used to investigate and regulate arsenic in water, but it is well understood that arsenic occurs in several chemical forms, and these exhibit different toxicities. It is problematic to use laboratory-based speciation techniques to assess exposure as it has been suggested that the distribution of species is not stable during transport in some types of samples. A method was developed in this study for the on-site speciation of the most toxic dissolved arsenic species: As (III), As (V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA). Development criteria included ease of use under field conditions, applicable at levels of concern for drinking water, and analytical performance. The approach is based on selective retention of arsenic species on specific ion-exchange chromatography cartridges followed by selective elution and quantification using graphite furnace atomic absorption spectroscopy. Water samples can be delivered to a set of three cartridges using either syringes or peristaltic pumps. Species distribution is stable at this point, and the cartridges can be transported to the laboratory for elution and quantitative analysis. A set of ten replicate spiked samples of each compound, having concentrations between 1 and 60 µg/L, were analyzed. Arsenic recoveries ranged from 78–112 % and relative standard deviations were generally below 10%. Resolution between species was shown to be outstanding, with the only limitation being that the capacity for As (V) was limited to approximately 50 µg/L. This could be easily remedied by changes in either cartridge design, or the extraction procedure. Recoveries were similar for two spiked hard groundwater samples indicating that dissolved minerals are not likely to be problematic. These results suggest that this methodology can be use for analysis of the four primary arsenic species of concern in

  20. Field Deployable Method for Arsenic Speciation in Water.

    PubMed

    Voice, Thomas C; Flores Del Pino, Lisveth V; Havezov, Ivan; Long, David T

    2011-01-01

    Contamination of drinking water supplies by arsenic is a world-wide problem. Total arsenic measurements are commonly used to investigate and regulate arsenic in water, but it is well understood that arsenic occurs in several chemical forms, and these exhibit different toxicities. It is problematic to use laboratory-based speciation techniques to assess exposure as it has been suggested that the distribution of species is not stable during transport in some types of samples. A method was developed in this study for the on-site speciation of the most toxic dissolved arsenic species: As (III), As (V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA). Development criteria included ease of use under field conditions, applicable at levels of concern for drinking water, and analytical performance.The approach is based on selective retention of arsenic species on specific ion-exchange chromatography cartridges followed by selective elution and quantification using graphite furnace atomic absorption spectroscopy. Water samples can be delivered to a set of three cartridges using either syringes or peristaltic pumps. Species distribution is stable at this point, and the cartridges can be transported to the laboratory for elution and quantitative analysis. A set of ten replicate spiked samples of each compound, having concentrations between 1 and 60 µg/L, were analyzed. Arsenic recoveries ranged from 78-112 % and relative standard deviations were generally below 10%. Resolution between species was shown to be outstanding, with the only limitation being that the capacity for As (V) was limited to approximately 50 µg/L. This could be easily remedied by changes in either cartridge design, or the extraction procedure. Recoveries were similar for two spiked hard groundwater samples indicating that dissolved minerals are not likely to be problematic. These results suggest that this methodology can be use for analysis of the four primary arsenic species of concern in

  1. Field deployable method for arsenic speciation in water

    NASA Astrophysics Data System (ADS)

    Voice, Thomas C.; Flores del Pino, Lisveth V.; Havezov, Ivan; Long, David T.

    Contamination of drinking water supplies by arsenic is a world-wide problem. Total arsenic measurements are commonly used to investigate and regulate arsenic in water, but it is well understood that arsenic occurs in several chemical forms, and these exhibit different toxicities. It is problematic to use laboratory-based speciation techniques to assess exposure as it has been suggested that the distribution of species is not stable during transport in some types of samples. A method was developed in this study for the on-site speciation of the most toxic dissolved arsenic species: As (III), As (V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA). Development criteria included ease of use under field conditions, applicable at levels of concern for drinking water, and analytical performance. The approach is based on selective retention of arsenic species on specific ion-exchange chromatography cartridges followed by selective elution and quantification using graphite furnace atomic absorption spectroscopy. Water samples can be delivered to a set of three cartridges using either syringes or peristaltic pumps. Species distribution is stable at this point, and the cartridges can be transported to the laboratory for elution and quantitative analysis. A set of ten replicate spiked samples of each compound, having concentrations between 1 and 60 μg/L, were analyzed. Arsenic recoveries ranged from 78% to 112% and relative standard deviations were generally below 10%. Resolution between species was shown to be outstanding, with the only limitation being that the capacity for As (V) was limited to approximately 50 μg/L. This could be easily remedied by changes in either cartridge design, or the extraction procedure. Recoveries were similar for two spiked hard groundwater samples indicating that dissolved minerals are not likely to be problematic. These results suggest that this methodology can be use for analysis of the four primary arsenic species of concern in

  2. Kinetic speciation and bioavailability of copper and nickel in mangrove sediments.

    PubMed

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Ramteke, Darwin; Chennuri, Kartheek

    2014-11-15

    An attempt was made to establish a mechanistic linkage between chemical speciation of copper and nickel, and their bioavailability in mangrove ecosystem. Kinetic speciation study was performed to determine the concentrations of labile metal-complexes and their dissociation rate constants in mangrove sediments. Concentrations of copper and nickel in the mangrove roots were used as indicators of their bioavailability. It was found that the bioaccumulation of both the metals gradually increased with the increasing concentrations of the labile metal complexes and their dissociation rate constants in the mangrove sediments. This study shows that concentration of labile metal (copper and nickel) complexes and their dissociation rate constants in mangrove sediment can be a good indicator of their bioavailability.

  3. Kinetic speciation and bioavailability of copper and nickel in mangrove sediments.

    PubMed

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Ramteke, Darwin; Chennuri, Kartheek

    2014-11-15

    An attempt was made to establish a mechanistic linkage between chemical speciation of copper and nickel, and their bioavailability in mangrove ecosystem. Kinetic speciation study was performed to determine the concentrations of labile metal-complexes and their dissociation rate constants in mangrove sediments. Concentrations of copper and nickel in the mangrove roots were used as indicators of their bioavailability. It was found that the bioaccumulation of both the metals gradually increased with the increasing concentrations of the labile metal complexes and their dissociation rate constants in the mangrove sediments. This study shows that concentration of labile metal (copper and nickel) complexes and their dissociation rate constants in mangrove sediment can be a good indicator of their bioavailability. PMID:25282180

  4. Speciation of Cd and Pb in dust emitted from sinter plant.

    PubMed

    Sammut, M L; Noack, Y; Rose, J; Hazemann, J L; Proux, O; Depoux, M; Ziebel, A; Fiani, E

    2010-01-01

    Many studies have provided evidence of the impact of heavy metals in atmospheric emission. Sinter plants represent the first step in steel production, and are important emitters of Cd and Pb. The toxicity of these two metals depends above all on their speciation. Particles collected before and after the filtration system were analysed to determine the Cd- and Pb-bearing phases, using analytical tools such as XRF, EXAFS or ICP-AES and chemical leaching (sequential extractions adapted to steel dusts). Results show that Pb is associated with carbonate and Cd with chloride. These two types of speciation lead to high solubility under common environmental conditions, which may produce impacts on the environment and health.

  5. Dynamics of aluminum speciation in forest-well drainage waters from the Rhode River watershed, Maryland.

    PubMed

    Bi, S P; An, S Q; Yang, M; Chen, T

    2001-05-01

    This paper reports an investigation of the dynamics of aluminum (Al) speciation in the forest-well waters from study site 110 of the Rhode River watershed, a representative sub-unit of Chesapeake Bay. Seasonal changes of Al speciation are evaluated by a modified MINEQL computer model using chemical equilibrium calculation. It was found that Al-F and Al-Org complexes were the dominate forms, whereas toxic forms of Al3+ and Al-OH were not significant. This indicates that Al toxicity is not very serious in the Rhode River area due to the high concentrations of fluoride and organic materials, even though sometimes pH is very low (approximately 4). Increased H+ or some other associated factors may be responsible for the decline in fish and amphibian population on the watershed.

  6. Sample preparation for arsenic speciation in terrestrial plants--a review.

    PubMed

    Amaral, Clarice D B; Nóbrega, Joaquim A; Nogueira, Ana R A

    2013-10-15

    Arsenic is an element widely present in nature. Additionally, it may be found as different species in several matrices and therefore it is one of the target elements in chemical speciation. Although the number of studies in terrestrial plants is low, compared to matrices such as fish or urine, this number is raising due to the fact that this type of matrix are closely related to the human food chain. In speciation analysis, sample preparation is a critical step and several extraction procedures present drawbacks. In this review, papers dealing with extraction procedures, analytical methods, and studies of species conservation in plants cultivated in terrestrial environment are critically discussed. Analytical procedures based on extractions using water or diluted acid solutions associated with HPLC-ICP-MS are good alternatives, owing to their versatility and sensitivity, even though less expensive strategies are shown as feasible choices. PMID:24054594

  7. Sample preparation for arsenic speciation in terrestrial plants--a review.

    PubMed

    Amaral, Clarice D B; Nóbrega, Joaquim A; Nogueira, Ana R A

    2013-10-15

    Arsenic is an element widely present in nature. Additionally, it may be found as different species in several matrices and therefore it is one of the target elements in chemical speciation. Although the number of studies in terrestrial plants is low, compared to matrices such as fish or urine, this number is raising due to the fact that this type of matrix are closely related to the human food chain. In speciation analysis, sample preparation is a critical step and several extraction procedures present drawbacks. In this review, papers dealing with extraction procedures, analytical methods, and studies of species conservation in plants cultivated in terrestrial environment are critically discussed. Analytical procedures based on extractions using water or diluted acid solutions associated with HPLC-ICP-MS are good alternatives, owing to their versatility and sensitivity, even though less expensive strategies are shown as feasible choices.

  8. Evaluation of Regenerated Catalyst for Mercury Speciation

    SciTech Connect

    Dennis Laudal

    2007-06-01

    In March of 2005, U.S. Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR). Mercury from coal-fired power plants was to be reduced from the current 48 to 38 tons/yr by 2010 and then 15 tons/yr by 2018. It is expected that the first phase reduction of {approx}21% will be achieved by cobenefits that will occur as a result of installing additional selective catalytic reduction (SCR) and flue gas desulfurization (FGD) systems to meet the new Clean Air Interstate Rule (CAIR). Detroit Edison (DTE) is installing SCR at all four units at its Monroe Station and will eventually install wet-FGD systems. As such, the Electric Power Research Institute (EPRI), the U.S. Department of Energy (DOE), and DTE have contracted with the Energy & Environmental Research Center (EERC) to determine the extent of mercury oxidation that occurs at Monroe Station. The EERC originally did mercury speciation sampling at Monroe Station in 2004 and then went back in 2005 to determine if any changes occurred as a result of catalyst aging. During the second test, in addition to measuring the mercury speciation at the inlet and outlet of the SCR, the EERC also completed sampling at a location between the catalyst layers. The results are shown in Table 1. In Table 1, the results show that {approx}40% of the Hg was in oxidized form (Hg{sup 2+}) at the inlet and nearly 100% Hg{sup 2+} at the outlet. The results at the midpoint were between 40% and 100%. As part of their overall strategy to reduce SCR costs, utilities and SCR vendors are attempting to regenerate catalyst layers that have degenerated over time. If these regenerated catalysts are used, the question remains as to the effect this process will have on the ability of these catalysts to oxidize mercury as well as reduce NO{sub x}. The current project is designed to measure the Hg speciation across an SCR using a regenerated catalyst. The results were compared to previous results to determine what, if any, changes

  9. Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola.

    PubMed

    Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo; Moisy, Philippe; Tribalat, Marie-Aude; Oberhaensli, François R; Dechraoui Bottein, Marie Yasmine; Thomas, Olivier P; Monfort, Marguerite; Moulin, Christophe; Den Auwer, Christophe

    2015-12-21

    The fate of radionuclides in the environment is a cause of great concern for modern society, seen especially in 2011 after the Fukushima accident. Among the environmental compartments, seawater covers most of the earth's surface and may be directly or indirectly impacted. The interaction between radionuclides and the marine compartment is therefore essential for better understanding the transfer mechanisms from the hydrosphere to the biosphere. This information allows for the evaluation of the impact on humans via our interaction with the biotope that has been largely undocumented up to now. In this report, we attempt to make a link between the speciation of heavy elements in natural seawater and their uptake by a model marine organism. More specifically, because the interaction of actinides with marine invertebrates has been poorly studied, the accumulation in a representative member of the Mediterranean coralligenous habitat, the sponge Aplysina cavernicola, was investigated and its uptake curve exposed to a radiotracer (241)Am was estimated using a high-purity Ge gamma spectrometer. But in order to go beyond the phenomenological accumulation rate, the speciation of americium(III) in seawater must be assessed. The speciation of (241)Am (and natural europium as its chemically stable surrogate) in seawater was determined using a combination of different techniques: Time-Resolved Laser-Induced Fluorescence (TRLIF), Extended X-ray Absorption Fine Structure (EXAFS) at the LIII edge, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and Scanning Electron Microscopy (SEM) and the resulting data were compared with the speciation modeling. In seawater, the americium(III) complex (as well as the corresponding europium complex, although with conformational differences) was identified as a ternary sodium biscarbonato complex, whose formula can be tentatively written as NaAm(CO3)2·nH2O. It is therefore this chemical form of americium that is

  10. Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola.

    PubMed

    Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo; Moisy, Philippe; Tribalat, Marie-Aude; Oberhaensli, François R; Dechraoui Bottein, Marie Yasmine; Thomas, Olivier P; Monfort, Marguerite; Moulin, Christophe; Den Auwer, Christophe

    2015-12-21

    The fate of radionuclides in the environment is a cause of great concern for modern society, seen especially in 2011 after the Fukushima accident. Among the environmental compartments, seawater covers most of the earth's surface and may be directly or indirectly impacted. The interaction between radionuclides and the marine compartment is therefore essential for better understanding the transfer mechanisms from the hydrosphere to the biosphere. This information allows for the evaluation of the impact on humans via our interaction with the biotope that has been largely undocumented up to now. In this report, we attempt to make a link between the speciation of heavy elements in natural seawater and their uptake by a model marine organism. More specifically, because the interaction of actinides with marine invertebrates has been poorly studied, the accumulation in a representative member of the Mediterranean coralligenous habitat, the sponge Aplysina cavernicola, was investigated and its uptake curve exposed to a radiotracer (241)Am was estimated using a high-purity Ge gamma spectrometer. But in order to go beyond the phenomenological accumulation rate, the speciation of americium(III) in seawater must be assessed. The speciation of (241)Am (and natural europium as its chemically stable surrogate) in seawater was determined using a combination of different techniques: Time-Resolved Laser-Induced Fluorescence (TRLIF), Extended X-ray Absorption Fine Structure (EXAFS) at the LIII edge, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and Scanning Electron Microscopy (SEM) and the resulting data were compared with the speciation modeling. In seawater, the americium(III) complex (as well as the corresponding europium complex, although with conformational differences) was identified as a ternary sodium biscarbonato complex, whose formula can be tentatively written as NaAm(CO3)2·nH2O. It is therefore this chemical form of americium that is

  11. Influence of population density on the concentration and speciation of metals in the soil and street dust from urban areas.

    PubMed

    Acosta, J A; Gabarrón, M; Faz, A; Martínez-Martínez, S; Zornoza, R; Arocena, J M

    2015-09-01

    Street dust and soil from high, medium and low populated cities and natural area were analysed for selected physical-chemical properties, total and chemical speciation of Zn, Pb, Cu, Cr, Cd, Co, Ni to understand the influence of human activities on metal accumulation and mobility in the environment. The pH, salinity, carbonates and organic carbon contents were similar between soil and dust from the same city. Population density increases dust/soil salinity but has no influence on metals concentrations in soils. Increases in metal concentrations with population density were observed in dusts. Cu, Zn, Pb, Cr can be mobilized more easily from dust compared to the soil. In addition, population density increase the percentage of Pb and Zn associated to reducible and carbonate phase in the dust. The behaviour of metals except Cd in soil is mainly affected by physico-chemical properties, while total metal influenced the speciation except Cr and Ni in dusts.

  12. Selenium speciation in ground water

    SciTech Connect

    Atalay, A.

    1990-07-10

    Selenium toxicity diseases in animals may occur when the intake exceeds 4 mg/kg and selenium deficiency symptoms may occur when dietary intake is less than 0.04 mg/kg. Since the selenium dietary requirement is very close to toxic concentration, it is important to understand the distribution of selenium in the environment. Selenium occurs in four oxidation states (-II, 0, +IV, and +VI) as selenide, elemental selenium, selenite and selenate. Selenate is reported as more soluble and less adsorbed than selenite. Selenate is more easily leached from soils and is the most available form for plants. Increased mobility of Se into the environment via anthropogenic activities, and the potential oxidation-reduction behavior of the element have made it imperative to study the aquatic chemistry of Se. For this purpose, Se species are divided into two different categories: dissolved Se (in material that passes through filters with 0.45 u openings) and particulate Se (in material of particle size > 0.45 mm) typically suspended sediment and other suspended solids. Element and colloidal phase, not truly dissolved, but passing through the filter is deemed to consist of selenium (-2,0). In dissolved state selenium may exist in three of its four oxidation states; Se(-II), Se(+IV), and Se(+VI). Particulate Se may exist in the same oxidation states as dissolved Se and can be found in different phases of the particulate matter. In sediments, Se may be within the organic material, iron and manganese oxides, carbonates or other mineral phases. The actual chemical forms of Se may be adsorbed to or coprecipitated with these phases (primarily selenite, SeO{sub 3}{sup 2{minus}}) and selenate, SeO{sub 4}{sup 2{minus}}. Selenide, Se(-II), can be covalently bound in the organic portion of a sediment. In addition, Se may be found in anoxic sediments as insoluble metal selenide precipitates, an insoluble elemental Se or as ferroselite (FeSe{sub 2}) and Se containing pyrite.

  13. Compositional dependence of sulfur speciation in Terrestrial and Martian magmas

    NASA Astrophysics Data System (ADS)

    Nash, William; Wood, Bernard; Smythe, Duane

    2016-04-01

    The capacity of magmas to transport sulfur from mantle to crust strongly influences a planet's surface chemistry. Sulfur is perhaps exceptional among the elements in the diversity of it's chemical speciation, exhibiting four redox species at geologically relevant conditions: sulfide (2-), elemental sulfur (0), sulfite (4+) and sulphate (6+). Furthermore, the solubility of sulfur in a magma (and hence the magma's capacity for delivering mantle-derived sulfur to the crust) depends critically on it's oxidation state. Our aim with this experimental study was to quantitatively determine the chemical speciation of sulfur within several common magmas, as a function of oxygen fugacity (fO2). We have performed a series of experiments on six sulfur-bearing silicate melts, which together represent a broad range of naturally occurring compositions: two putative Martian basalts, two terrestrial MORBs (one primitive, one evolved), an andesite, and a dacite. These melts were equilibrated together (at one-atmosphere pressure, 1300°C) with various CO-CO2-SO2 gas mixtures, which imposed a range of fO2s. This range spanned -2 to +1.6 log units (relative to the Quartz-Fayalite-Magnetite or QFM buffer), and the step-size was 0.25 log units. The quenched glasses were analyzed by X-ray Absorption Spectroscopy (specifically XANES) at the Diamond synchrotron (UK), and the spectra obtained were used to determine the species of sulfur present in each glass. The chemical composition of each glass (including their sulfur contents) was characterized by electron-probe microanalysis. Despite the generally low concentrations of sulfur in our glasses (never exceeding 0.24 wt%), we have clearly resolved the crossover between reduced (S2-) and oxidized (S6+) species for three of our basalts. The other three melts yielded more noisy XANES spectra, and as a result their redox crossovers are visible, but less clearly resolved. For every melt composition, the redox crossover is a continuous (though

  14. Mercury speciation analysis in terrestrial animal tissues.

    PubMed

    Berzas Nevado, J J; Rodríguez Martín-Doimeadios, R C; Guzmán Bernardo, F J; Rodríguez Fariñas, N; Patiño Ropero, M J

    2012-09-15

    No previous analytical procedures are available and validated for mercury speciation analysis in terrestrial animal tissues. This analysis is a difficult task both because the expected concentrations are low, since important accumulation process are not likely to occur, and also because there are not commercially available certified reference material. Thus, an analytical methodology has been developed and validated for mercury speciation for the specific case of terrestrial animal tissues. The proposed method is based on the quantitative extraction of the species by closed-vessel microwave assisted heating with an alkaline reagent, followed by ethylation. The ethylated derivatives were then submitted to head-space solid phase microextraction with a 100 μm polidimethylsiloxane-coated fiber, and desorbed onto a gas chromatograph coupled to atomic fluorescence detection via pyrolysis unit (HS-SPME-GC-pyro-AFS). Procedural detection limits were 31.8 ng g(-1) and 52.5 ng g(-1) for CH(3)Hg(+) and Hg(2+), respectively, for liver and 35.3 ng g(-1) and 58.1 ng g(-1) for CH(3)Hg(+) and Hg(2+), respectively, for kidney. These limits of detection are 5.5 and 6 times better than the obtained without solid phase microextraction for CH(3)Hg(+) and Hg(2+), respectively. The methodology was found linear up to 120 μg L(-1) and reproducible from one day to the following. It was validated with certified reference materials NCS ZC 71001 (beef liver) and BCR No 186 (pig kidney) for total mercury, calculated as the sum of species, and with spiked red deer liver and kidney for speciation. Finally, it was applied to the analysis of samples of red deer liver, red deer kidney and wild boar kidney coming from the Almadén's mercury mining area (Ciudad Real, Spain), the longest and largest producer of mercury in the world until its closure in 2002. PMID:22967634

  15. Plutonium Speciation, Solubilization and Migration in Soils

    SciTech Connect

    Neu, M.; Runde, W.

    1999-06-01

    This report summarizes research completed in the first half of a three-year project. As outlined in the authors' proposal they are focusing on (1) characterizing the plutonium at an actinide contaminated site, RFETS, including determining the origin, dispersion, and speciation of the plutonium, (2) studying environmentally important plutonium complexes, primarily hydroxides and carbonates, and (3) examining the interactions of plutonium species with manganese minerals. In the first year the authors focused on site based studies. This year they continue to characterize samples from the RFETS, study the formation and structural and spectroscopic features of environmentally relevant Pu species, and begin modeling the environmental behavior of plutonium.

  16. Chemoselective Boronic Ester Synthesis by Controlled Speciation**

    PubMed Central

    Fyfe, James W B; Seath, Ciaran P; Watson, Allan J B

    2014-01-01

    Control of boronic acid solution speciation is presented as a new strategy for the chemoselective synthesis of boronic esters. Manipulation of the solution equilibria within a cross-coupling milieu enables the formal homologation of aryl and alkenyl boronic acid pinacol esters. The generation of a new, reactive boronic ester in the presence of an active palladium catalyst also facilitates streamlined iterative catalytic C=C bond formation and provides a method for the controlled oligomerization of sp2-hybridized boronic esters. PMID:25267096

  17. Chapter A5. Section 6.4.A. Arsenic Speciation

    USGS Publications Warehouse

    Garbarino, John R.

    2005-01-01

    Two sample-processing methods (field speciation and laboratory speciation) used at the USGS National Water Quality Laboratory (NWQL) are specific to sample analysis by inductively coupled plasma-mass spectrometry (ICP-MS) for determining the concentration of inorganic and organic arsenic species in a water sample. The field-speciation method requires NWQL Schedule 1729. The laboratory-speciation method requires use either of NWQL Schedule 1730, 1731, or 1732, as appropriate for study objectives. For either the field- or laboratory-speciation method, prior knowledge is needed of sample matrix-composition characteristics (that is, major-ion concentrations in filtered samples). Major-ion data are necessary to determine (1) the volume of ethylenediaminetetraacetic acid (EDTA) that will be required for sample preservation, and (2) if sample dilution is required.

  18. Speciation analysis of Arsenic from Contaminated Soils and Plants from an abandoned mine in Korea

    NASA Astrophysics Data System (ADS)

    Yoon, H.; Yoon, C.

    2008-12-01

    The analytical technique for true separation of different chemical species such as arsenic has been challenging in contaminated environmental samples because of their importance in environmental toxicity. Arsenic species can be transformed rapidly by slight changes in redox condition during experimental manipulation. It has been documented frequently by researchers including USEPA to standardize the analytical technique for arsenic from many environmental samples. The toxicity of elements depends not only on their total concentrations but also on their chemical forms. In real environment where arsenic was considered as contaminant, we often experience difficulty in measuring mobility of them from constituent soils. Compare to the previously documented techniques, measurement of total concentration, analytical techniques often called hyphenated or hybrid for analyzing different chemical species are being suggested and is regarded as essential method to resolve toxicities of different species. The reference materials with different mineral composition were selected and used. One is composed of mostly with Al-silicate minerals and another is mostly composed with calcite and ferrosilite. This study focuses on analytical method in order to set a research system for environmental assessment and restoration for general use. Various hyphenated analytical techniques for the speciation of toxic elements of interest must be preceded which is now expert in KBSI for collaborative researches. Speciation analysis results show that metals toxicity in different chemical species such as arsenic can be resolved.

  19. Application of Hyphenated Techniques in Speciation Analysis of Arsenic, Antimony, and Thallium

    PubMed Central

    Michalski, Rajmund; Szopa, Sebastian; Jabłońska, Magdalena; Łyko, Aleksandra

    2012-01-01

    Due to the fact that metals and metalloids have a strong impact on the environment, the methods of their determination and speciation have received special attention in recent years. Arsenic, antimony, and thallium are important examples of such toxic elements. Their speciation is especially important in the environmental and biomedical fields because of their toxicity, bioavailability, and reactivity. Recently, speciation analytics has been playing a unique role in the studies of biogeochemical cycles of chemical compounds, determination of toxicity and ecotoxicity of selected elements, quality control of food products, control of medicines and pharmaceutical products, technological process control, research on the impact of technological installation on the environment, examination of occupational exposure, and clinical analysis. Conventional methods are usually labor intensive, time consuming, and susceptible to interferences. The hyphenated techniques, in which separation method is coupled with multidimensional detectors, have become useful alternatives. The main advantages of those techniques consist in extremely low detection and quantification limits, insignificant interference, influence as well as high precision and repeatability of the determinations. In view of their importance, the present work overviews and discusses different hyphenated techniques used for arsenic, antimony, and thallium species analysis, in different clinical, environmental and food matrices. PMID:22654649

  20. Dissolved iron and its speciation in a shallow eutrophic lake and its inflowing rivers.

    PubMed

    Nagai, Takashi; Imai, Akio; Matsushige, Kazuo; Yokoi, Kunihiko; Fukushima, Takehiko

    2007-02-01

    It has been suggested that iron is a limiting factor on bloom-forming cyanobacteria in lake water. Although the availability of iron for phytoplankton depends significantly on its speciation, little is known about iron speciation in natural lake water. We investigated the horizontal distribution and temporal variation of dissolved iron and its chemical speciation in Lake Kasumigaura and its two inflowing rivers. Concentrations of dissolved iron and its organic ligands, determined by cathodic stripping voltammetry, clearly decreased as lake water flowed from the river entry points toward the center of the lake, indicating their riverine origin. The fraction of iron occurring in organic complexes tended to increase with the water flow. These results suggest that most of the dissolved iron in river water forms unstable soluble species, such as inorganic iron; thus, these unstable iron species may be scavenged in the mouths of rivers, and stable organic complexes of iron may flow to the center of the lake. Furthermore, most of the dissolved iron (88.2-99.9%) was present as organic complexes, and the inorganic iron level in Lake Kasumigaura (pFe' value=7.8-13.6) was similar to that observed in the open ocean. This result suggests that iron is an important factor determining the structure of the phytoplankton community in Lake Kasumigaura.

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

    USGS Publications Warehouse

    Rimondi, Valentina; Bardelli, Fabrizio; Benvenuti, Marco; Costagliola, Pilario; Gray, John E.; Lattanzi, Pierfranco

    2014-01-01

    A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl2, HgO and Hg0, were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

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

    SciTech Connect

    F Claret; C Tournassat; C Crouzet; E Gaucher; T Schäfer; G Braibant; D Guyonnet

    2011-12-31

    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 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.

  3. Selenium Speciation and Management in Wet FGD Systems

    SciTech Connect

    Searcy, K; Richardson, M; Blythe, G; Wallschlaeger, D; Chu, P; Dene, C

    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, trace 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

  4. Bio-metals imaging and speciation in cells using proton and synchrotron radiation X-ray microspectroscopy

    PubMed Central

    Ortega, Richard; Devès, Guillaume; Carmona, Asunción

    2009-01-01

    The direct detection of biologically relevant metals in single cells and of their speciation is a challenging task that requires sophisticated analytical developments. The aim of this article is to present the recent achievements in the field of cellular chemical element imaging, and direct speciation analysis, using proton and synchrotron radiation X-ray micro- and nano-analysis. The recent improvements in focusing optics for MeV-accelerated particles and keV X-rays allow application to chemical element analysis in subcellular compartments. The imaging and quantification of trace elements in single cells can be obtained using particle-induced X-ray emission (PIXE). The combination of PIXE with backscattering spectrometry and scanning transmission ion microscopy provides a high accuracy in elemental quantification of cellular organelles. On the other hand, synchrotron radiation X-ray fluorescence provides chemical element imaging with less than 100 nm spatial resolution. Moreover, synchrotron radiation offers the unique capability of spatially resolved chemical speciation using micro-X-ray absorption spectroscopy. The potential of these methods in biomedical investigations will be illustrated with examples of application in the fields of cellular toxicology, and pharmacology, bio-metals and metal-based nano-particles. PMID:19605403

  5. Sexual signaling and speciation, a microevolutionary perspective.

    PubMed

    Boake, Christine R B

    2002-11-01

    Despite the growing evidence that sexual selection can drive speciation, the evolution of sexual signals in natural populations is far from being well-understood. Sexual signals evolve in response to a variety of factors. Some of the most important selective factors are conspecifics, transmission efficiency in a particular environment, detection by predators, and phylogenetic constraints. These factors have been addressed quite successfully in studies of single types of signals in both vertebrates and invertebrates. However, it is less clear how multimodal signals evolve because the factors listed above will act on every component of the signaling system, and the relative weights of each type of signal must be taken into account. Species of Drosophila are excellent for such analyses because they are amenable to both phenotypic experimentation and genetic manipulation. This paper presents an approach that involves two analyses: studies of which signals are sexually selected within a species, and parallel studies of the signals that are involved in behavioral isolation between closely related species. If the same signal characteristics are involved in both processes, they would provide support for the hypothesis that sexual selection can drive speciation. This approach is illustrated with studies of Hawaiian Drosophila and a review of signals that could be sexually selected in Drosophila melanogaster.

  6. Pleistocene speciation in the genus Populus (salicaceae).

    PubMed

    Levsen, Nicholas D; Tiffin, Peter; Olson, Matthew S

    2012-05-01

    The macroevolutionary consequences of recent climate change remain controversial, and there is little paleobotanical or morphological evidence that Pleistocene (1.8-0.12 Ma) glacial cycles acted as drivers of speciation, especially among lineages with long generation times, such as trees. We combined genetic and ecogeographic data from 2 closely related North American tree species, Populus balsamifera and P. trichocarpa (Salicacaeae), to determine if their divergence coincided with and was possibly caused by Pleistocene climatic events. We analyzed 32 nuclear loci from individuals of P. balsamifera and P. trichocarpa to produce coalescent-based estimates of the divergence time between the 2 species. We coupled the coalescent analyses with paleodistribution models to assess the influence of climate change on species' range. Furthermore, measures of niche overlap were used to investigate patterns of ecological differentiation between species. We estimated the divergence date of P. balsamifera and P. trichocarpa at approximately 75 Ka, which corresponds closely with the onset of Marine Isotope Stage 4 (∼76 Ka) and a rapid increase in global ice volume. Significance tests of niche overlap, in conjunction with genetic estimates of migration, suggested that speciation occurred in allopatry, possibly resulting from the environmental effects of Pleistocene glacial cycles. Our results indicate that the divergence of keystone tree species, which have shaped community diversity in northern North American ecosystems, was recent and may have been a consequence of Pleistocene-era glaciation and climate change.

  7. Gene regulation and speciation in house mice

    PubMed Central

    Mack, Katya L.; Campbell, Polly; Nachman, Michael W.

    2016-01-01

    One approach to understanding the process of speciation is to characterize the genetic architecture of post-zygotic isolation. As gene regulation requires interactions between loci, negative epistatic interactions between divergent regulatory elements might underlie hybrid incompatibilities and contribute to reproductive isolation. Here, we take advantage of a cross between house mouse subspecies, where hybrid dysfunction is largely unidirectional, to test several key predictions about regulatory divergence and reproductive isolation. Regulatory divergence between Mus musculus musculus and M. m. domesticus was characterized by studying allele-specific expression in fertile hybrid males using mRNA-sequencing of whole testes. We found extensive regulatory divergence between M. m. musculus and M. m. domesticus, largely attributable to cis-regulatory changes. When both cis and trans changes occurred, they were observed in opposition much more often than expected under a neutral model, providing strong evidence of widespread compensatory evolution. We also found evidence for lineage-specific positive selection on a subset of genes related to transcriptional regulation. Comparisons of fertile and sterile hybrid males identified a set of genes that were uniquely misexpressed in sterile individuals. Lastly, we discovered a nonrandom association between these genes and genes showing evidence of compensatory evolution, consistent with the idea that regulatory interactions might contribute to Dobzhansky-Muller incompatibilities and be important in speciation. PMID:26833790

  8. A genomic perspective on hybridization and speciation

    PubMed Central

    Payseur, Bret A.; Rieseberg, Loren H.

    2016-01-01

    Hybridization among diverging lineages is common in nature. Genomic data provide a special opportunity to characterize the history of hybridization and the genetic basis of speciation. We review existing methods and empirical studies to identify recent advances in the genomics of hybridization, as well as issues that need to be addressed. Notable progress has been made in the development of methods for detecting hybridization and inferring individual ancestries. However, few approaches reconstruct the magnitude and timing of gene flow, estimate the fitness of hybrids or incorporate knowledge of recombination rate. Empirical studies indicate that the genomic consequences of hybridization are complex, including a highly heterogeneous landscape of differentiation. Inferred characteristics of hybridization differ substantially among species groups. Loci showing unusual patterns – which may contribute to reproductive barriers – are usually scattered throughout the genome, with potential enrichment in sex chromosomes and regions of reduced recombination. We caution against the growing trend of interpreting genomic variation in summary statistics across genomes as evidence of differential gene flow. We argue that converting genomic patterns into useful inferences about hybridization will ultimately require models and methods that directly incorporate key ingredients of speciation, including the dynamic nature of gene flow, selection acting in hybrid populations and recombination rate variation. PMID:26836441

  9. Physicochemical speciation of molybdenum in rain water.

    PubMed

    Kawakubo, S; Hashi, S; Iwatsuki, M

    2001-07-01

    A combination of a sensitive catalytic determination method with filtration and ultrafiltration has been used for the physicochemical speciation of molybdenum in natural and synthetic rain water samples. The concentration (CL) of labile molybdenum was evaluated by a direct catalytic determination. The total concentration (CT ) of molybdenum was determined after the acid decomposition of the sample to calculate the non-labile concentration (CT-CL). From the speciation results, molybdenum species in the successive rainfall sample were found in a fraction with smaller molecular weights < 10(3) Da and characterized as labile forms, i.e. simple molybdate ions. Non-labile molybdenum existed in particulate matter (> or = 0.45 microm in particle size) and distributed predominantly in the initial rainfall sample. The coprecipitation with Fe(III) hydroxide contributed to the formation of the non-labile molybdenum. In the initial rainfall sample, a small part of molybdenum was labile in the particle fraction (> or = 0.45 microm). This type of molybdenum was associated with the formation of humic iron aggregates.

  10. Mercury speciation by CE: an update.

    PubMed

    Kubán, Petr; Pelcová, Pavlína; Margetínová, Jana; Kubán, Vlastimil

    2009-01-01

    This review provides an update on mercury speciation by CE. It includes a brief discussion on physicochemical properties, toxicity and transformation pathways of mercury species (i.e. methyl-, ethyl-, phenyl- and inorganic mercury) and outlines recent trends in Hg speciation by CE. CE is presented as a complementary technique to chromatographic separation techniques, especially in cases when speed, high efficiency and low sample volumes are required. The development of suitable sample preconcentration/isolation (sample stacking, ion exchange, liquid-liquid-liquid extraction, dual-cloud point extraction) to achieve low LODs for analysis of trace concentrations of mercury species in real samples is emphasized. Hyphenation of CE to element specific detectors (i.e. electrothermal atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry) is discussed as well as a potential of CE in interaction studies that may provide useful information on interaction of various Hg species with selected bio-macromolecules.

  11. Pleistocene Speciation in the Genus Populus (Salicaceae)

    PubMed Central

    Levsen, Nicholas D.; Tiffin, Peter; Olson, Matthew S.

    2012-01-01

    The macroevolutionary consequences of recent climate change remain controversial, and there is little paleobotanical or morphological evidence that Pleistocene (1.8–0.12 Ma) glacial cycles acted as drivers of speciation, especially among lineages with long generation times, such as trees. We combined genetic and ecogeographic data from 2 closely related North American tree species, Populus balsamifera and P. trichocarpa (Salicacaeae), to determine if their divergence coincided with and was possibly caused by Pleistocene climatic events. We analyzed 32 nuclear loci from individuals of P. balsamifera and P. trichocarpa to produce coalescent-based estimates of the divergence time between the 2 species. We coupled the coalescent analyses with paleodistribution models to assess the influence of climate change on species' range. Furthermore, measures of niche overlap were used to investigate patterns of ecological differentiation between species. We estimated the divergence date of P. balsamifera and P. trichocarpa at approximately 75 Ka, which corresponds closely with the onset of Marine Isotope Stage 4 (∼76 Ka) and a rapid increase in global ice volume. Significance tests of niche overlap, in conjunction with genetic estimates of migration, suggested that speciation occurred in allopatry, possibly resulting from the environmental effects of Pleistocene glacial cycles. Our results indicate that the divergence of keystone tree species, which have shaped community diversity in northern North American ecosystems, was recent and may have been a consequence of Pleistocene-era glaciation and climate change. PMID:22213709

  12. Alternative adaptations, speciation, and phylogeny (A Review)

    PubMed Central

    West-Eberhard, Mary Jane

    1986-01-01

    Alternative adaptations—different adaptive phenotypes maintained in the same life stage and the same population but not necessarily simultaneously expressed in the same individual—represent contrasting character sets produced by the same genome, in effect allowing a single species to occupy more than one sympatric niche. Such alternatives are particularly likely to give rise to novel adaptations because of selection for extreme dissimilarity between them and because established traits buffer populations against extinction while independently expressed alternatives evolve in new directions. Particular alternatives can be suddenly fixed in populations with little or no genetic change, leading to a period of rapid evolution (especially, of morphology) exaggerating the characteristics of the newly fixed form. This burst of change would facilitate rapid speciation and could produce “punctuated” patterns of evolution. Evidence from a wide variety of organisms shows that alternative phenotypes are exceedingly common in nature and that they are probably important in speciation and macroevolution. Although many of these ideas and observations have been noted piecemeal by previous authors, bringing them together demonstrates the probable importance of alternative adaptations in the origin of major evolutionary novelties and calls for a revision of current and traditional ideas about the role of behavior and ontogeny in the genesis of organic diversity. PMID:16578790

  13. Foliar or root exposures to smelter particles: consequences for lead compartmentalization and speciation in plant leaves.

    PubMed

    Schreck, Eva; Dappe, Vincent; Sarret, Géraldine; Sobanska, Sophie; Nowak, Dorota; Nowak, Jakub; Stefaniak, Elżbieta Anna; Magnin, Valérie; Ranieri, Vincent; Dumat, Camille

    2014-04-01

    In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb-cell wall and Pb-organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the

  14. PILOT-SCALE EVALUATION OF THE IMPACT OF SELECTIVE CATALYTIC REDUCTION FOR NOx ON MERCURY SPECIATION

    SciTech Connect

    Dennis L. Laudal; John H. Pavlish; Kevin C. Galbreath; Jeffrey S. Thompson; Gregory F. Weber; Everett Sondreal

    2000-12-01

    Full-scale tests in Europe and bench-scale tests in the United States have indicated that the catalyst, normally vanadium/titanium metal oxide, used in the selective catalytic reduction (SCR) of NO{sub x}, may promote the formation of Hg{sup 2+} and/or particulate-bound mercury (Hg{sub p}). To investigate the impact of SCR on mercury speciation, pilot-scale screening tests were conducted at the Energy & Environmental Research Center. The primary research goal was to determine whether the catalyst or the injection of ammonia in a representative SCR system promotes the conversion of Hg{sup 0} to Hg{sup 2+} and/or Hg{sub p} and, if so, which coal types and parameters (e.g., rank and chemical composition) affect the degree of conversion. Four different coals, three eastern bituminous coals and a Powder River Basin (PRB) subbituminous coal, were tested. Three tests were conducted for each coal: (1) baseline, (2) NH{sub 3} injection, and (3) SCR of NO{sub x}. Speciated mercury, ammonia slip, SO{sub 3}, and chloride measurements were made to determine the effect the SCR reactor had on mercury speciation. It appears that the impact of SCR of NO{sub x} on mercury speciation is coal-dependent. Although there were several confounding factors such as temperature and ammonia concentrations in the flue gas, two of the eastern bituminous coals showed substantial increases in Hg{sub p} at the inlet to the ESP after passing through an SCR reactor. The PRB coal showed little if any change due to the presence of the SCR. Apparently, the effects of the SCR reactor are related to the chloride, sulfur and, possibly, the calcium content of the coal. It is clear that additional work needs to be done at the full-scale level.

  15. Determination of phosphorus speciation in dairy manure using XRD and XANES spectroscopy.

    PubMed

    Güngör, Kerem; Jürgensen, Astrid; Karthikeyan, K G

    2007-01-01

    Intensive manure application is an important source of diffuse phosphorus (P) pollution. Phosphorus availability from animal manure is influenced by its chemical speciation. The major objective of this study was to investigate the P speciation in raw and anaerobically digested dairy manure with an emphasis on the calcium (Ca) and magnesium (Mg) phosphate phases. Influent and effluent from an on-farm digester in Wisconsin were sampled and sieved, and the 25 to 53 microm size fraction was dried for X-ray powder diffraction (XRD) and P K-edge X-ray absorption near edge structure (XANES) analyses. Struvite (MgNH4PO4.6H2O) was identified in both the raw (influent) and anaerobically digested (effluent) manure using XRD. Qualitative analysis of P K-edge XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite (CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57.0 and 43.0% of P was associated with DCPA and struvite, respectively, in the raw manure. In the anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with hydroxylapatite (HAp). The P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate (aq-PO4), newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P K-edge XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure. PMID:17965388

  16. Foliar or root exposures to smelter particles: consequences for lead compartmentalization and speciation in plant leaves.

    PubMed

    Schreck, Eva; Dappe, Vincent; Sarret, Géraldine; Sobanska, Sophie; Nowak, Dorota; Nowak, Jakub; Stefaniak, Elżbieta Anna; Magnin, Valérie; Ranieri, Vincent; Dumat, Camille

    2014-04-01

    In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb-cell wall and Pb-organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the

  17. Speciation Dynamics of Phosphorus during (Hydro)Thermal Treatments of Sewage Sludge.

    PubMed

    Huang, Rixiang; Tang, Yuanzhi

    2015-12-15

    (Hydro)thermal treatments of sewage sludge from wastewater treatment process can significantly reduce waste volume and transform sludge into valuable products such as pyrochar and hydrochar. Given the global concern with phosphorus (P) resource depletion, P recycling/reclamation from or direct soil application of the derived chars can be potential P recycling practices. In order to evaluate P recyclability as well as the selection and optimization of treatment techniques, it is critical to understand the effects of different treatment techniques and conditions on P speciation and distribution. In the present study, we systematically characterized P speciation in chars derived from thermal (i.e., pyrolysis) and hydrothermal treatments of municipal sewage sludge using complementary chemical extraction and nuclear magnetic resonance (NMR) spectroscopy methods. P species in the raw activated sludge was dominated by orthophosphate and long-chain polyphosphates, whereas increased amounts of pyrophosphate and short-chain polyphosphates formed after pyrolysis at 250-600 °C. In contrast, hydrothermal treatments resulted in the production of only inorganic orthophosphate in the hydrochar. In addition to the change of molecular speciation, thermal treatments also altered the physical state and extractability of different P species in the pyrochars from pyrolysis, with both total P and polyphosphate being less extractable with increasing pyrolysis temperature. Results from this study suggest that P speciation and availability in sludge-derived chars are tunable by varying treatment techniques and conditions, and provide fundamental knowledge basis for the design and selection of waste management strategies for better nutrient (re)cycling and reclamation.

  18. Interaction of As and Sb in the hyperaccumulator Pteris vittata L.: changes in As and Sb speciation by XANES.

    PubMed

    Wan, Xiaoming; Lei, Mei; Chen, Tongbin

    2016-10-01

    Arsenic (As) and antimony (Sb) are chemical analogs that display similar characteristics in the environment. The As hyperaccumulator Pteris vittata L. is a potential As-Sb co-accumulating species. However, when this plant is exposed to different As and Sb speciation, the associated accumulating mechanisms and subsequent assimilation processes of As and Sb remain unclear. A 2-week hydroponic experiment was conducted by exposing P. vittata to single AsIII, AsV, SbIII, and SbV or the co-existence of AsIII and SbIII and AsV and SbV. P. vittata could co-accumulate As and Sb in the pinna (>1000 mg kg(-1)) with high translocation (>1) of As and Sb from the root to the pinna. P. vittata displayed apparent preference to the trivalent speciation of As and Sb than to the pentavalent speciation. Under the single exposure of AsIII or SbIII, the pinna concentration of As and Sb was 84 and 765 % higher than that under the single exposure of AsV or SbV, respectively. Despite the provided As speciation, the main speciation of As in the root was AsV, whereas the main speciation of As in the pinna was AsIII. The Sb in the roots comprised SbV and SbIII when exposed to SbV but was exclusively SbIII when exposed to SbIII. The Sb in the pinna was a mixture of SbV and SbIII regardless of the provided Sb speciation. Compared with the single exposure of As, the co-existence of As and Sb increased the As concentration in the pinna of P. vittata by 50-66 %, accompanied by a significant increase in the AsIII percentage in the root. Compared with the single exposure of Sb, the co-existence of Sb and As also increased the Sb concentration in the pinna by 51-100 %, but no significant change in Sb speciation was found in P. vittata. PMID:27351876

  19. DEVELOPMENT OF FINE PARTICULATE EMISSION FACTORS AND SPECIATION PROFILES FOR OIL AND GAS-FIRED COMBUSTION SYSTEMS

    SciTech Connect

    Glenn C. England; Stephanie Wien; Mingchih O. Chang

    2002-08-01

    This report provides results from the first year of this three-year project to develop dilution measurement technology for characterizing PM2.5 (particles with aerodynamic diameter smaller than 2.5 micrometers) and precursor emissions from stationary combustion sources used in oil, gas and power generation operations. Detailed emission rate and chemical speciation test results for a refinery gas-fired process heater and plans for cogeneration gas turbine tests and pilot-scale tests are presented. Tests were performed using a research dilution sampling apparatus and traditional EPA methods to compare PM2.5 mass and chemical speciation. Test plans are presented for a gas turbine facility that will be tested in the fourth quarter of 2002. A preliminary approach for pilot-scale tests is presented that will help define design constraints for a new dilution sampler design that is smaller, lighter, and less costly to use.

  20. 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...

  1. 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...

  2. 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...

  3. Cascade ultrafiltration and competing ligand exchange for kinetic speciation of aluminium, iron, and nickel in fresh water.

    PubMed

    Hassan, Nouri M; Murimboh, John D; Sekaly, Amina L R; Mandal, Rupasri; Chakrabarti, Chuni L; Grégoire, D Conrad

    2006-04-01

    Kinetic speciation of nickel, aluminium, and iron in fresh water has been investigated by cascade ultrafiltration followed by competing ligand exchange of the ultrafiltered fractions. Graphite furnace atomic absorption spectrometry was used to measure the kinetics of metal complex dissociation. Dissolved metal species were fractionated by cascade ultrafiltration. Metal speciation in each ultrafiltered fraction was then characterized as free metal ions, "labile" metal complexes (with dissociation rate constants >/=10(-3) s(-1)), "slowly labile" metal complexes (with dissociation rate constants >10(-6) s(-1)), and "inert" metal complexes (with dissociation rate constants <10(-6) s(-1)). The experimental results were compared with the predictions of a computer-based equilibrium speciation model, the Windermere humic aqueous model (WHAM) V. Cascade ultrafiltration coupled with kinetic speciation of the metal species in each molecular weight cut-off (MWCO) fraction provided a more comprehensive picture and insight into the physical and the chemical characteristics of the metal species than either ultrafiltration or measurement of dissociation kinetics alone.

  4. Duel cobalt speciation in Co/ZSM-5 catalysts

    SciTech Connect

    Stencel, J.M.; Rao, V.U.S.; Diehl, J.R.; Rhee, K.H.; Dhere, A.G.; DeAngelis, R.J.

    1983-11-01

    X-ray diffraction, x-ray photoelectron sepctroscopy, and infrared spectroscopy are used to investigate cobalt speciation in Co/ZSM-5 catalysts containing 1.4 to 9.5 wt % cobalt. These catalysts, metal-impregnated using incipient wetness techniques with Co(NO/sub 3/)/sub 2/ . 6H/sub 2/O, are shown to contain highly dispersed ion-exchanged, non-reducible Co/sup 2 +/ species interior to the ZSM-5, and large, reducible cobalt oxide crystallites on the exterior of the ZSM-5 crystallite surface. The number of Co/sup 2 +/ ions located inside a unit cell of ZSM-5 and the number of pyridine molecules that coordinately bond to each of these ions are estimated by using infrared data characterizing pyridine chemisorption. The crystalline forms of cobalt on the surface of the ZSM-5 are identified and their sizes estimated after O/sub 2/ calcination, H/sub 2/ reduction, and CO + H/sub 2/ exposure. These data are then scrutinized for correlations of chemical and physical properties of the Co/ZSM-5 catalysts with conversion activity and selectivity for synthesis of hydrocarbons from CO + H/sub 2/ gas. 15 references, 5 figures, 3 tables.

  5. Dual cobalt speciation in Co/ZSM-5 catalysts

    SciTech Connect

    Stencel, J.M.; Rao, V.U.S.; Diehl, J.R.; Rhee, K.H.; Dhere, A.G.; DeAngelis, R.J.

    1983-01-01

    X-Ray diffraction, X-ray photoelectron spectroscopy, and infrared spectroscopy are used to investigate cobalt speciation in Co/ZSM-5 catalysts containing 1.4 to 9.5 wt% cobalt. These catalysts, metal-impregnated using incipient wetness techniques with Co(NO/sub 3/)/sub 2/ x 6H/sub 2/O, are shown to contain highly dispersed, ion-exchanged, non-reducible Co/sup 2 +/ species interior to the ZSM-5, and large, reducible cobalt oxide crystallites on the exterior of the ZSM-5 crystallite surface. The number of Co/sup 2 +/ ions located inside a unit cell of ZSM-5 and the number of pyridine molecules that coordinately bond to each of these ions are estimated by using infrared data characterizing pyridine chemisorption. The crystalline forms of cobalt on the surface of the ZSM-5 are identified and their sizes estimated after O/sub 2/ calcination, H/sub 2/ reduction, and CO + H/sub 2/ exposure. These data are then scrutinized for correlations of chemical and physical properties of the Co/ZSM-5 catalysts with conversion activity and selectivity for synthesis of hydrocarbons from CO + H/sub 2/ gas. 15 references, 5 figures, 3 tables.

  6. Demonstrated Potential of Ion Mobility Spectrometry for Detection of Adulterated Perfumes and Plant Speciation

    SciTech Connect

    Clark, Jared Matthew; Daum, Keith Alvin; Kalival, J. H.

    2003-01-01

    This initial study evaluates the use of ion mobility spectrometry (IMS) as a rapid test procedure for potential detection of adulterated perfumes and speciation of plant life. Sample types measured consist of five genuine perfumes, two species of sagebrush, and four species of flowers. Each sample type is treated as a separate classification problem. It is shown that discrimination using principal component analysis with K-nearest neighbors can distinguish one class from another. Discriminatory models generated using principal component regressions are not as effective. Results from this examination are encouraging and represent an initial phase demonstrating that perfumes and plants possess characteristic chemical signatures that can be used for reliable identification.

  7. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    SciTech Connect

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

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy’s (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (i) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (ii) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (iii) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  8. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION.

    SciTech Connect

    FRANCIS, A.J.; DODGE, C.J.

    2006-11-16

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  9. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    SciTech Connect

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

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  10. The uptake and speciation of various Al species in the Brassica rapa pekinensis.

    PubMed

    Polak, T B; Milacic, R; Pihlar, B; Mitrović, B

    2001-05-01

    An investigation was carried out on the uptake and speciation of Al species in Al tolerant Chinese cabbage (Brassica rapa L. ssp. pekinensis). Plants were exposed to 10 microg cm(-3) of Al in the chemical forms of Al3+, Al-citrate and Al-malate in a time span from 1 up to 24 h. In each experiment the nutrient solution and stem sap were analysed by a combination of FPLC ICP AES and ES MS MS techniques. Speciation analysis enabled determination of particular chemical forms of Al present in the nutrient solution or in stem sap. The results indicate that Al3+ added to the nutrient solution remained as Al3+ in the solution during the experiments, but in the roots transformation to Al-malate occurred. Al was transported from roots to the upper parts of the plant as Al-malate (70%) and Al3+ (30%). Al-citrate or Al-malate added to the nutrient solution were transferred to the upper parts of the plant without transformation of their chemical forms.

  11. An improved equilibrium-kinetics speciation algorithm for redox reactions in variably saturated subsurface flow systems

    NASA Astrophysics Data System (ADS)

    Xu, Tianfu; Pruess, Karsten; Brimhall, George

    1999-07-01

    Reactive chemical transport occurs in a variety of geochemical environments, and over a broad range of space and time scales. Efficiency of the chemical speciation and water-rock-gas interaction calculations is important for modeling field-scale multidimensional reactive transport problems. An improved efficient model, REACT, for simulating water-rock-gas interaction under equilibrium and kinetic conditions, has been developed. In this model, equilibrium and kinetic reactions are solved simultaneously by Newton-Raphson iteration. The REACT speciation model was coupled with the multidimensional nonisothermal multiphase flow and mass transport code TOUGH2, resulting in the general purpose reactive chemical transport simulator TOUGHREACT. An application to supergene copper enrichment of a typical copper protore that includes the sulfide minerals pyrite (FeS 2) and chalcopyrite (CuFeS 2) is presented. The efficiency and convergence of the present model is demonstrated from this numerically difficult application that involves very large variations in the concentrations of oxygen, and sulfide and sulfate species. TOUGHREACT provides a detailed description of water-rock-gas interactions during fully transient, multiphase, nonisothermal flow and transport in hydrologically and geochemically heterogeneous media. The code is helpful for assessment of acid mine drainage remediation, geothermal convection, waste disposal, contaminant transport and water quality.

  12. A Japanese view on speciation: "Sumiwake" explosive speciation of the cichlids in Lake Victoria.

    PubMed

    Kawamiya, Nobuo

    2003-01-01

    Imanishi's "mental" (cerebral) view of speciation is presented, in Mizuhata's revision. The key concept here is the "ethological partition" of the species. Members of each species=society (etho-species) share the same mental (brain) software, irrespective of their genetic structure. Cerebral animals perform active programmed selection, not to be confused with passive, non-programmed "natural selection" as in Neo-Darwinism. The program includes mating-choice of peculiar characters, distinct from the Neo-Darwinian sexual selection supposed due to the specific choosy genes. Speciation can occur, as a "partition of species=society", with bifurcation of mate-choosing program in the parent species. A main promoter for this bifurcation is species-specific "passion" for especially significant characters: long necks, ornamental antlers, ocelli feathers, bright nuptial colors etc. The cichlids in Lake Victoria achieved explosive speciation, while retaining their genetic homogeneity completely. Therefore it is illogical to attribute this divergence to extraordinary mutations in "action controlling genes". The origin of species=society (etho-species) can trace along to the Cambrian Period.

  13. Characterization of Speciated Aerosol Direct Radiative Forcing Over California

    SciTech Connect

    Zhao, Chun; Leung, Lai-Yung R.; Easter, Richard C.; Hand, Jenny; Avise, J.

    2013-03-16

    A fully coupled meteorology-chemistry model (WRF-Chem) with added capability of diagnosing the spatial and seasonal distribution of radiative forcings for individual aerosol species over California is used to characterize the radiative forcing of speciated aerosols in California. Model simulations for the year of 2005 are evaluated with various observations including meteorological data from California Irrigation Management Information System (CIMIS), aerosol mass concentrations from US EPA Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE), and aerosol optical depth from AErosol RObotic NETwork (AERONET) and satellites. The model well captures the observed seasonal meteorological conditions over California. Overall, the simulation is able to reproduce the observed spatial and seasonal distribution of mass concentration of total PM2.5 and the relative contribution from individual aerosol species, except the model significantly underestimates the surface concentrations of organic matter (OM) and elemental carbon (EC), potentially due to uncertainty in the anthropogenic emissions of OM and EC and the outdated secondary organic aerosol mechanism used in the model. A sensitivity simulation with anthropogenic EC emission doubled significantly reduces the model low bias of EC. The simulation reveals high anthropogenic aerosol loading over the Central Valley and the Los Angeles metropolitan regions and high natural aerosol (dust) loading over southeastern California. The seasonality of aerosol surface concentration is mainly determined by vertical turbulent mixing, ventilation, and photochemical activity, with distinct characteristics for individual aerosol species and between urban and rural areas. The simulations show that anthropogenic aerosols dominate the aerosol optical depth (AOD). The ratio of AOD to AAOD (aerosol absorption optical depth) shows distinct seasonality with a winter maximum and a summer minimum

  14. Genetics of ecological divergence during speciation

    PubMed Central

    Arnegard, Matthew E.; McGee, Matthew D.; Matthews, Blake; Marchinko, Kerry B.; Conte, Gina L.; Kabir, Sahriar; Bedford, Nicole; Bergek, Sara; Chan, Yingguang Frank; Jones, Felicity C.; Kingsley, David M.; Peichel, Catherine L.; Schluter, Dolph

    2014-01-01

    Ecological differences often evolve early in speciation as divergent natural selection drives adaptation to distinct ecological niches, leading ultimately to reproductive isolation. Though this process is a major generator of biodiversity, its genetic basis remains poorly understood. Here we investigate the genetic architecture of niche differentiation in a sympatric species pair of threespine stickleback fish by mapping the environment-dependent effects of phenotypic traits on hybrid feeding and performance under semi-natural conditions. We show that multiple, unlinked loci act largely additively to determine position along the major niche axis separating these recently diverged species. We also find that functional mismatch between phenotypic traits reduces growth of some stickleback hybrids beyond that expected from an intermediate phenotype, suggesting a role for epistasis between the underlying genes. This functional mismatch might lead to hybrid incompatibilities that are analogous to those underlying intrinsic reproductive isolation but that depend on the ecological context. PMID:24909991

  15. Horizontal Gene Transfer, Dispersal and Haloarchaeal Speciation

    PubMed Central

    Papke, R. Thane; Corral, Paulina; Ram-Mohan, Nikhil; de la Haba, Rafael R.; Sánchez-Porro, Cristina; Makkay, Andrea; Ventosa, Antonio

    2015-01-01

    The Halobacteria are a well-studied archaeal class and numerous investigations are showing how their diversity is distributed amongst genomes and geographic locations. Evidence indicates that recombination between species continuously facilitates the arrival of new genes, and within species, it is frequent enough to spread acquired genes amongst all individuals in the population. To create permanent independent diversity and generate new species, barriers to recombination are probably required. The data support an interpretation that rates of evolution (e.g., horizontal gene transfer and mutation) are faster at creating geographically localized variation than dispersal and invasion are at homogenizing genetic differences between locations. Therefore, we suggest that recurrent episodes of dispersal followed by variable periods of endemism break the homogenizing forces of intrapopulation recombination and that this process might be the principal stimulus leading to divergence and speciation in Halobacteria. PMID:25997110

  16. Mercury speciation in the Adriatic Sea.

    PubMed

    Kotnik, Jože; Horvat, Milena; Ogrinc, Nives; Fajon, Vesna; Žagar, Dušan; Cossa, Daniel; Sprovieri, Francesca; Pirrone, Nicola

    2015-07-15

    Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM – dissolved gaseous Hg, RHg – reactive Hg, THg – total Hg, MeHg – monomethyl Hg and DMeHg – dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data.

  17. Sulfur speciation in individual aerosol particles

    NASA Astrophysics Data System (ADS)

    Neubauer, Kenneth R.; Sum, Stephen T.; Johnston, Murray V.; Wexler, Anthony S.

    1996-08-01

    Sulfur aerosols play an important role in acid deposition and the Earth's energy balance. Important species in these aerosols include methanesulfonates, hydroxymethanesulfonates, sulfates, and sulfites. Because the relative amounts of these species indicate different sources and atmospheric processes, it is important to distinguish them in single-aerosol particles. To accomplish this task, we use rapid single-particle mass spectrometry (RSMS), a technique that permits individual particles to be analyzed in an online mode. Each sulfur species produces a characteristic set of ions in the mass spectra. In simulated marine and urban aerosols the relative amounts of methanesulfonic acid (MSA) and sodium hydroxymethanesulfonate (NaHMSA) in a single particle can be determined from peak area ratios in the mass spectra. Improved quantitation is possible by application of the classification and regression tree (CART) algorithm to distinguish the mass spectra of particles having different compositions. Factors that influence speciation include particle size, morphology, and laser fluence.

  18. Horizontal gene transfer, dispersal and haloarchaeal speciation.

    PubMed

    Papke, R Thane; Corral, Paulina; Ram-Mohan, Nikhil; Haba, Rafael R de la; Sánchez-Porro, Cristina; Makkay, Andrea; Ventosa, Antonio

    2015-01-01

    The Halobacteria are a well-studied archaeal class and numerous investigations are showing how their diversity is distributed amongst genomes and geographic locations. Evidence indicates that recombination between species continuously facilitates the arrival of new genes, and within species, it is frequent enough to spread acquired genes amongst all individuals in the population. To create permanent independent diversity and generate new species, barriers to recombination are probably required. The data support an interpretation that rates of evolution (e.g., horizontal gene transfer and mutation) are faster at creating geographically localized variation than dispersal and invasion are at homogenizing genetic differences between locations. Therefore, we suggest that recurrent episodes of dispersal followed by variable periods of endemism break the homogenizing forces of intrapopulation recombination and that this process might be the principal stimulus leading to divergence and speciation in Halobacteria. PMID:25997110

  19. Mercury speciation in the Adriatic Sea.

    PubMed

    Kotnik, Jože; Horvat, Milena; Ogrinc, Nives; Fajon, Vesna; Žagar, Dušan; Cossa, Daniel; Sprovieri, Francesca; Pirrone, Nicola

    2015-07-15

    Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM – dissolved gaseous Hg, RHg – reactive Hg, THg – total Hg, MeHg – monomethyl Hg and DMeHg – dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data. PMID:26013591

  20. Competitive speciation in quantitative genetic models.

    PubMed

    Drossel, B; Mckane, A

    2000-06-01

    We study sympatric speciation due to competition in an environment with a broad distribution of resources. We assume that the trait under selection is a quantitative trait, and that mating is assortative with respect to this trait. Our model alternates selection according to Lotka-Volterra-type competition equations, with reproduction using the ideas of quantitative genetics. The recurrence relations defined by these equations are studied numerically and analytically. We find that when a population enters a new environment, with a broad distribution of unexploited food sources, the population distribution broadens under a variety of conditions, with peaks at the edge of the distribution indicating the formation of subpopulations. After a long enough time period, the population can split into several subpopulations with little gene flow between them. PMID:10816369

  1. Arsenic distribution and speciation in Daphnia pulex.

    PubMed

    Caumette, Guilhem; Koch, Iris; Moriarty, Maeve; Reimer, Kenneth J

    2012-08-15

    Rat Lake, Yellowknife, Northwest Territories, is situated on arsenic-rich tailings from a historical gold mine. The abundant zooplankton species Daphnia pulex in this lake was used to study the impact of arsenic at the base of the freshwater food web; the speciation and distribution of arsenic in D. pulex and its food sources; and the origin of formation of organoarsenicals in freshwater systems. The arsenic concentration in lake water was measured as 0.25 mg L(-1), while the zooplankton organisms contained up to 35 mg kg(-1) d.w. arsenic. Plankton samples were analyzed for arsenic speciation, by using X-ray Absorption Near Edge Structure (XANES) on the whole, dried samples and High Performance Liquid Chromatography coupled to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) on water extracts. XANES data suggest that D. pulex mainly contain inorganic arsenicals with 56% of arsenic with +5 oxidation state and 10% of arsenic with +3 oxidation state, but also 34% of organoarsenic compounds that were identified with HPLC-ICP-MS as monomethylarsonate (MMA), dimethylarsinate (DMA), and arsenosugars. The most abundant of the organoarsenicals was the glycerol sugar (Sugar 1). X-ray Fluorescence (XRF) mapping of D. pulex for arsenic distribution showed that arsenic was mainly distributed in the gut of the animal, where its concentration was ten times higher than in the surrounding tissues. Moreover, the analysis of residues from extractions targeting water-soluble and lipid-soluble arsenicals suggested that part of the measured arsenic signal comes from ingested sediments, phytoplankton, or other food sources. These food sources contain inorganic arsenic only, with As(V)-O in phytoplankton and As(III)-S in sediments, suggesting the possibility that the organoarsenicals compounds detected in the tissues of the organism are created by the Daphnia. PMID:22750169

  2. Mimicry: developmental genes that contribute to speciation.

    PubMed

    Naisbit, Russell E; Jiggins, Chris D; Mallet, James

    2003-01-01

    Despite renewed interest in the role of natural selection as a catalyst for the origin of species, the developmental and genetic basis of speciation remains poorly understood. Here we describe the genetics of Müllerian mimicry in Heliconius cydno and H. melpomene (Lepidoptera: Nymphalidae), sister species that recently diverged to mimic other Heliconius. This mimetic shift was a key step in their speciation, leading to pre- and postmating isolation. We identify 10 autosomal loci, half of which have major effects. At least eight appear to be homologous with genes known to control pattern differences within each species. Dominance has evolved under the influence of identifiable "modifier" loci rather than being a fixed characteristic of each locus. Epistasis is found at many levels: phenotypic interaction between specific pairs of genes, developmental canalization due to polygenic modifiers so that patterns are less sharply defined in hybrids, and overall fitness through ecological selection against nonmimetic hybrid genotypes. Most of the loci are clustered into two genomic regions or "supergenes," suggesting color pattern evolution is constrained by preexisting linked elements that may have arisen via tandem duplication rather than having been assembled by natural selection. Linkage, modifiers, and epistasis affect the strength of mimicry as a barrier to gene flow between these naturally hybridizing species and may permit introgression in genomic regions unlinked to those under disruptive selection. Müllerian mimics in Heliconius use different genetic architectures to achieve the same mimetic patterns, implying few developmental constraints. Therefore, although developmental and genomic constraints undoubtedly influence the evolutionary process, their effects are probably not strong in comparison with natural selection.

  3. A mechanistic accounting of SOM speciation and kinetics in soils

    NASA Astrophysics Data System (ADS)

    Maggi, F.; Riley, W. J.; Guerry, N.; Torn, M. S.; Kleber, M.

    2012-12-01

    The nature and dynamics of soil organic matter (SOM) are arguably far from being understood and accurately represented in current site, regional, and global land use and climate models. Whereas consolidated models make use of aggregated pools describing SOM with characteristic turnover times such as inert, passive, slow cycling, and fast cycling, or linking the turnover time to the molecular weight of the compound, recent analyses of SOM below the top soil suggest that those approaches only partially capture SOM dynamics, and that SOM stability may largely be determined by biological and chemical protection as well as other environmental factors rather than the molecular structure of the compound and its molecular weight. We introduce here a new paradigm of SOM speciation and kinetics that explicitly decouples the assumed recalcitrance and turnover time from the SOM molecular density and structure in favour of a mechanistic accounting of microbially mediated processes and chemo-physical interactions among the various SOM species and soil environment. These processes include microbial assimilation, respiration and C recycling; depolymerization of solid litter, root exudates, and dead cells into various decomposed SOM groups; and incorporation of soluble SOM species into a protected phase not available to chemical and biological agents. SOM was described by means of functional compounds including mono- and polysaccharides, lignin, amino compounds, organic acids, nucleic acids, lipids, and phenols, each being accounted for by one or more representative species in the model. Fungal and bacterial microbial functional groups were used to characterize depolymerization and respiration rates. The SOM reaction network and characteristics, its mathematical inclusion within the TOUGHREACT framework, and some preliminary results of modeling grasslands and forested ecosystems are presented here. Biogeochemical reaction network of SOC pathways. Steady state vertical contentration

  4. Application of chemometric analysis and self Organizing Map-Artificial Neural Network as source receptor modeling for metal speciation in river sediment.

    PubMed

    Pandey, Mayank; Pandey, Ashutosh Kumar; Mishra, Ashutosh; Tripathi, B D

    2015-09-01

    Present study deals with the river Ganga water quality and its impact on metal speciation in its sediments. Concentration of physico-chemical parameters was highest in summer season followed by winter and lowest in rainy season. Metal speciation study in river sediments revealed that exchangeable, reducible and oxidizable fractions were dominant in all the studied metals (Cr, Ni, Cu, Zn, Cd, Pb) except Mn and Fe. High pollution load index (1.64-3.89) recommends urgent need of mitigation measures. Self-organizing Map-Artificial Neural Network (SOM-ANN) was applied to the data set for the prediction of major point sources of pollution in the river Ganga.

  5. 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

  6. Dynamic speciation analysis and bioavailability of metals in aquatic systems.

    PubMed

    van Leeuwen, Herman P; Town, Raewyn M; Buffle, Jacques; Cleven, Rob F M J; Davison, William; Puy, Jaume; van Riemsdijk, Willem H; Sigg, Laura

    2005-11-15

    Dynamic metal speciation analysis in aquatic ecosystems is emerging as a powerful basis for development of predictions of bioavailability and reliable risk assessment strategies. A given speciation sensor is characterized by an effective time scale or kinetic window that defines the measurable metal species via their labilities. Here we review the current state of the art for the theory and application of dynamic speciation sensors. We show that a common dynamic interpretation framework, based on rigorous flux expressions incorporating the relevant diffusion and reaction steps, is applicable for a suite of sensors that span a range of time scales. Interpolation from a kinetic spectrum of speciation data is proposed as a practical strategy for addressing questions of bioavailability. Case studies illustrate the practical significance of knowledge on the dynamic features of metal complex species in relation to biouptake, and highlight the limitations of equilibrium-based models. PMID:16323747

  7. PARTICLE SPECIATION AND EMISSION PROFILES OF SMALL 2-STROKE ENGINES

    EPA Science Inventory

    The Human Exposure and Atmospheric Sciences Division (HEASD) conducts studies designed to acquire information from emission sources for use in source apportionment studies. The objective of this work is to characterize a complete, speciated emission profile (PM and air toxics) ...

  8. Male competition fitness landscapes predict both forward and reverse speciation.

    PubMed

    Keagy, Jason; Lettieri, Liliana; Boughman, Janette W

    2016-01-01

    Speciation is facilitated when selection generates a rugged fitness landscape such that populations occupy different peaks separated by valleys. Competition for food resources is a strong ecological force that can generate such divergent selection. However, it is unclear whether intrasexual competition over resources that provide mating opportunities can generate rugged fitness landscapes that foster speciation. Here we use highly variable male F2 hybrids of benthic and limnetic threespine sticklebacks, Gasterosteus aculeatus Linnaeus, 1758, to quantify the male competition fitness landscape. We find that disruptive sexual selection generates two fitness peaks corresponding closely to the male phenotypes of the two parental species, favouring divergence. Most surprisingly, an additional region of high fitness favours novel hybrid phenotypes that correspond to those observed in a recent case of reverse speciation after anthropogenic disturbance. Our results reveal that sexual selection through male competition plays an integral role in both forward and reverse speciation.

  9. Speciation, Ecological Opportunity, and Latitude (American Society of Naturalists Address).

    PubMed

    Schluter, Dolph

    2016-01-01

    Evolutionary hypotheses to explain the greater numbers of species in the tropics than the temperate zone include greater age and area, higher temperature and metabolic rates, and greater ecological opportunity. These ideas make contrasting predictions about the relationship between speciation processes and latitude, which I elaborate and evaluate. Available data suggest that per capita speciation rates are currently highest in the temperate zone and that diversification rates (speciation minus extinction) are similar between latitudes. In contrast, clades whose oldest analyzed dates precede the Eocene thermal maximum, when the extent of the tropics was much greater than today, tend to show highest speciation and diversification rates in the tropics. These findings are consistent with age and area, which is alone among hypotheses in predicting a time trend. Higher recent speciation rates in the temperate zone than the tropics suggest an additional response to high ecological opportunity associated with low species diversity. These broad patterns are compelling but provide limited insights into underlying mechanisms, arguing that studies of speciation processes along the latitudinal gradient will be vital. Using threespine stickleback in depauperate northern lakes as an example, I show how high ecological opportunity can lead to rapid speciation. The results support a role for ecological opportunity in speciation, but its importance in the evolution of the latitudinal gradient remains uncertain. I conclude that per capita evolutionary rates are no longer higher in the tropics than the temperate zone. Nevertheless, the vast numbers of species that have already accumulated in the tropics ensure that total rate of species production remains highest there. Thus, tropical evolutionary momentum helps to perpetuate the steep latitudinal biodiversity gradient.

  10. Solid/solution Cu fractionations/speciation of a Cu contaminated soil after pilot-scale electrokinetic remediation and their relationships with soil microbial and enzyme activities.

    PubMed

    Wang, Quan-Ying; Zhou, Dong-Mei; Cang, Long; Li, Lian-Zhen; Wang, Peng

    2009-01-01

    The aim of this study was to investigate the detailed metal speciation/fractionations of a Cu contaminated soil before and after electrokinetic remediation as well as their relationships with the soil microbial and enzyme activities. Significant changes in the exchangeable and adsorbed-Cu fractionations occurred after electrokinetic treatment, while labile soil Cu in the solution had a tendency to decrease from the anode to the cathode, and the soil free Cu(2+) ions were mainly accumulated in the sections close to the cathode. The results of regression analyses revealed that both the soil Cu speciation in solution phase and the Cu fractionations in solid phase could play important roles in the changes of the soil microbial and enzyme activities. Our findings suggest that the bioavailability of soil heavy metals and their ecotoxicological effects on the soil biota before and after electroremediation can be better understood in terms of their chemical speciation and fractionations. PMID:19427727

  11. How humans drive speciation as well as extinction

    PubMed Central

    Maron, M.

    2016-01-01

    A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation—and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon ‘no net loss’ conservation literature—considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. PMID:27358365

  12. Geographical range and speciation in fossil and living molluscs.

    PubMed Central

    Jablonski, David; Roy, Kaustuv

    2003-01-01

    The notion of a positive relation between geographical range and speciation rate or speciation probability may go back to Darwin, but a negative relation between these parameters is equally plausible. Here, we test these alternatives in fossil and living molluscan taxa. Late Cretaceous gastropod genera exhibit a strong negative relation between the geographical ranges of constituent species and speciation rate per species per million years; this result is robust to sampling biases against small-bodied taxa and is not attributable to phylogenetic effects. They also exhibit weak inverse or non-significant relations between geographical range and (i) the total number of species produced over the 18 million year timeframe, and (ii) the number of species in a single timeplane. Sister-group comparisons using extant molluscan species also show a non-significant relation between median geographical range and species richness of genera. These results support the view that the factors promoting broad geographical ranges also tend to damp speciation rates. They also demonstrate that a strong inverse relation between per-species speciation rate and geographical range need not be reflected in analyses conducted within a single timeplane, underscoring the inadequacy of treating net speciation as a proxy for raw per-taxon rates. PMID:12639320

  13. How humans drive speciation as well as extinction.

    PubMed

    Bull, J W; Maron, M

    2016-06-29

    A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation-and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon 'no net loss' conservation literature-considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. PMID:27358365

  14. Speciation in birds: Genes, geography, and sexual selection

    PubMed Central

    Edwards, Scott V.; Kingan, Sarah B.; Calkins, Jennifer D.; Balakrishnan, Christopher N.; Jennings, W. Bryan; Swanson, Willie J.; Sorenson, Michael D.

    2005-01-01

    Molecular studies of speciation in birds over the last three decades have been dominated by a focus on the geography, ecology, and timing of speciation, a tradition traceable to Mayr's Systematics and the Origin of Species. However, in the recent years, interest in the behavioral and molecular mechanisms of speciation in birds has increased, building in part on the older traditions and observations from domesticated species. The result is that many of the same mechanisms proffered for model lineages such as Drosophila—mechanisms such as genetic incompatibilities, reinforcement, and sexual selection—are now being seriously entertained for birds, albeit with much lower resolution. The recent completion of a draft sequence of the chicken genome, and an abundance of single-nucleotide polymorphisms on the autosomes and sex chromosomes, will dramatically accelerate research on the molecular mechanisms of avian speciation over the next few years. The challenge for ornithologists is now to inform well studied examples of speciation in nature with increased molecular resolution—to clone speciation genes if they exist—and thereby evaluate the relative roles of extrinsic, intrinsic, deterministic, and stochastic causes for avian diversification. PMID:15851678

  15. Speciation and distribution of cadmium and lead in salinized horizons of antrosols

    NASA Astrophysics Data System (ADS)

    Bulgariu, D.; Bulgariu, L.; Astefanei, D.

    2009-04-01

    The utilization of intensive technologies for the vegetable cultivation in glass houses by the administration of high doses of organic fertilizes, the supra-dimensional irrigation and the maintaining of soil at high humidity state, in special in case of vicious drainage have as result the rapid degradation of morphological, chemical and physical characteristics of soils, concretized by: (i) decrease of structural aggregates stability; (ii) more dense packing of soil; (iii) accumulation of easy soluble salts (in special at superior horizons level); (iv) limitation of organic compounds and micro-elements biodisponibility. All these determined a significant reduction of productivity and of exploitation duration of soils from glass houses. These phenomena modified continuously the dynamic of speciation processes and inter-phases distribution, of heavy metals in soils from glass houses, and can determined a non-controlled accumulation of heavy metals, in special as mobile forms with high biodisponibility. Ours studied have been performed using soil profiles drawing from Copou-glass house, Iasi (Romania). Has been followed the modification of distribution for speciation forms of cadmium and lead (two heavy metals with high toxicity degree), between hortic antrosol horizons, and between chemical-mineralogical components of this, with the progressive salinization of superior horizons, in 2007-2008 period. The separation, differentiation and determination of cadmium and lead speciation forms was done by combined solid-liquid sequential extraction (SPE) and extraction in aqueous polymer-inorganic salt two-phase systems (ABS) procedure, presented in some of ours previous studies. After extraction, the total contents of the two heavy metals and fractions from these differential bonded by mineral and organic components of hortic antrosol have been determined by atomic absorption spectrometry. The specific interaction mechanisms of Cd and Pb with organic-mineral components of

  16. Sulfur speciation in natural hydrothermal waters, Iceland

    NASA Astrophysics Data System (ADS)

    Kaasalainen, Hanna; Stefánsson, Andri

    2011-05-01

    The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH T was between 2.20 and 9.30 at the discharge temperature and the SO 4 and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg -1, respectively. The analyses were carried out on-site within ˜10 min of sampling using ion chromatography (IC) for sulfate (SO 42-), thiosulfate (S 2O 32-) and polythionates (S xO 62-) and titration and/or colorimetry for total dissolved sulfide (S 2-). Sulfite (SO 32-) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S 2- were detected in all samples with concentrations of 0.02-52.7 mmol kg -1 and <1-4100 μmol kg -1, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg -1 (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg -1. Thiosulfate and SO 32- were not detected in <100 °C well waters and S 2O 32- was observed only at low concentrations (<1-8 μmol kg -1) in ˜200 °C well waters. In alkaline and neutral pH hot springs, S 2O 32- was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S TOT). In steam-heated acid-sulfate waters, S 2O 32- was not a significant sulfur species. The results demonstrate that S 2O 32- and SO 32- do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ˜200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O 2, S 2- is degassed and

  17. Microanalytical X-ray imaging of depleted uranium speciation in environmentally aged munitions residues.

    PubMed

    Crean, Daniel E; Livens, Francis R; Stennett, Martin C; Grolimund, Daniel; Borca, Camelia N; Hyatt, Neil C

    2014-01-01

    Use of depleted uranium (DU) munitions has resulted in contamination of the near-surface environment with penetrator residues. Uncertainty in the long-term environmental fate of particles produced by impact of DU penetrators with hard targets is a specific concern. In this study DU particles produced in this way and exposed to the surface terrestrial environment for longer than 30 years at a U.K. firing range were characterized using synchrotron X-ray chemical imaging. Two sites were sampled: a surface soil and a disposal area for DU-contaminated wood, and the U speciation was different between the two areas. Surface soil particles showed little extent of alteration, with U speciated as oxides U3O7 and U3O8. Uranium oxidation state and crystalline phase mapping revealed these oxides occur as separate particles, reflecting heterogeneous formation conditions. Particles recovered from the disposal area were substantially weathered, and U(VI) phosphate phases such as meta-ankoleite (K(UO2)(PO4) · 3H2O) were dominant. Chemical imaging revealed domains of contrasting U oxidation state linked to the presence of both U3O7 and meta-ankoleite, indicating growth of a particle alteration layer. This study demonstrates that substantial alteration of DU residues can occur, which directly influences the health and environmental hazards posed by this contamination. PMID:24451034

  18. Localization and speciation of arsenic and trace elements in rice tissues

    SciTech Connect

    Smith, Euan; Kempson, Ivan; Juhasz, Albert L.; Weber, John; Skinner, William M.; Gräfe, Markus

    2009-09-14

    The consumption of arsenic (As) contaminated rice is an important exposure route for humans in countries where rice cultivation employs As contaminated irrigation water. Arsenic toxicity and mobility are a function of its chemical-speciation. The distribution and identification of As in the rice plant are hence necessary to determine the uptake, transformation and potential risk posed by As contaminated rice. In this study we report on the distribution and chemical-speciation of As in rice (Oryza sativa Quest) by X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) measurements of rice plants grown in As contaminated paddy water. Investigations of {mu}XRF images from rice tissues found that As was present in all rice tissues, and its presence correlated with the presence of iron at the root surface and copper in the rice leaf. X-ray absorption near edge structure analysis of rice tissues identified that inorganic As was the predominant form of As in all rice tissues studied, and that arsenite became increasingly dominant in the aerial portion of the rice plant.

  19. Localization and speciation of arsenic and trace elements in rice tissues.

    PubMed

    Smith, Euan; Kempson, Ivan; Juhasz, Albert L; Weber, John; Skinner, William M; Gräfe, Markus

    2009-07-01

    The consumption of arsenic (As) contaminated rice is an important exposure route for humans in countries where rice cultivation employs As contaminated irrigation water. Arsenic toxicity and mobility are a function of its chemical-speciation. The distribution and identification of As in the rice plant are hence necessary to determine the uptake, transformation and potential risk posed by As contaminated rice. In this study we report on the distribution and chemical-speciation of As in rice (Oryza sativa Quest) by X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) measurements of rice plants grown in As contaminated paddy water. Investigations of muXRF images from rice tissues found that As was present in all rice tissues, and its presence correlated with the presence of iron at the root surface and copper in the rice leaf. X-ray absorption near edge structure analysis of rice tissues identified that inorganic As was the predominant form of As in all rice tissues studied, and that arsenite became increasingly dominant in the aerial portion of the rice plant. PMID:19345396

  20. Synchrotron Speciation of Silver and Zinc Oxide Nanoparticles Aged in a Kaolin Suspension

    SciTech Connect

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

    2010-07-23

    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{sup 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.

  1. Assessment of occupational exposure to inorganic arsenic based on urinary concentrations and speciation of arsenic.

    PubMed Central

    Farmer, J G; Johnson, L R

    1990-01-01

    An analytical speciation method, capable of separating inorganic arsenic (As (V), As (III] and its methylated metabolites (MMAA, DMAA) from common, inert, dietary organoarsenicals, was applied to the determination of arsenic in urine from a variety of workers occupationally exposed to inorganic arsenic compounds. Mean urinary arsenic (As (V) + As (III) + MMAA + DMAA) concentrations ranged from 4.4 micrograms/g creatinine for controls to less than 10 micrograms/g for those in the electronics industry, 47.9 micrograms/g for timber treatment workers applying arsenical wood preservatives, 79.4 micrograms/g for a group of glassworkers using arsenic trioxide, and 245 micrograms/g for chemical workers engaged in manufacturing and handling inorganic arsenicals. The maximum recorded concentration was 956 micrograms/g. For the most exposed groups, the ranges in the average urinary arsenic speciation pattern were 1-6% As (V), 11-14% As (III), 14-18% MMAA, and 63-70% DMAA. The highly raised urinary arsenic concentrations for the chemical workers, in particular, and some glassworkers are shown to correspond to possible atmospheric concentrations in the workplace and intakes in excess of, or close to, recommended and statutory limits and those associated with inorganic arsenic related diseases. PMID:2357455

  2. PM2.5 Characterization for Time Series Studies: Pointwise Uncertainty Estimation and Bulk Speciation Methods Applied in Denver

    PubMed Central

    Dutton, Steven J.; Schauer, James J.; Vedal, Sverre; Hannigan, Michael P.

    2009-01-01

    Many studies have identified associations between adverse health effects and short-term exposure to particulate matter less than 2.5 microns in diameter (PM2.5). These effects, however, are not consistent across geographical regions. This may be due in part to variations in the chemical make-up of PM2.5 resulting from unique combinations of sources, both primary and secondary, in different regions. The Denver Aerosol Sources and Health (DASH) study is a multi-year time series study designed to characterize the daily chemical composition of PM2.5 in Denver, identify the major contributing sources, and investigate associations between sources and a broad array of adverse health outcomes. Measurement methodology, field blank correction, pointwise uncertainty estimation and detection limit consideration are discussed in the context of bulk speciation for the DASH study. Results are presented for the first 4.5 years of mass, inorganic ion and bulk carbon speciation. The derived measurement uncertainties were propagated using the root sum of squares method and show good agreement with precision estimates derived from bi-weekly duplicate samples collected on collocated samplers. Gravimetric mass has the most uncertainty of any measurement and reconstructed mass generated from the sum of the individual species shows less uncertainty than measured mass on average. The methods discussed provide a good framework for PM2.5 speciation measurements and are generalizable to analysis of other environmental measures. PMID:20126292

  3. Enabling in-situ observation of organic aerosol speciated composition: Advances in TAG instrumentation (Invited)

    NASA Astrophysics Data System (ADS)

    Goldstein, A. H.; Worton, D. R.; Zhao, Y.; Kreisberg, N. M.; Teng, A. P.; Hering, S. V.; Gorecki, T.; Ranjan, M.; Hennigan, C. J.; Lambe, A.; Nguyen, N.; Donahue, N. M.; Robinson, A. L.; Jayne, J. T.; Williams, B. J.; Worsnop, D. R.

    2009-12-01

    The complex chemical composition of atmospheric aerosols, particularly the organic carbon portion, presents unique measurement challenges. We developed the Thermal Desorption Aerosol Gas chromatograph (TAG) system for hourly in-situ speciation of a wide range of primary and secondary organic compounds in aerosols. This instrument combines an impactor particle collector with thermal desorption followed by gas chromatography and mass spectrometric detection to provide separation, identification, and quantification of organic constituents at the molecular level. Observed compounds include alkanes, aldehydes, ketones, PAHs, monocarboxylic acids, and many more. The hourly time resolution measurements provided by TAG capture dynamic and frequent changes in aerosol composition that would not be resolved using traditional filter collection. TAG measurements also provide a much larger data set, facilitating the use of statistical approaches such as positive matrix factorization to identify source categories and their contributions to the total observed aerosol. Because TAG identifies organic compounds at the molecular level, it can build on the extensive work obtained by traditional GC/MS analysis of filter samples on source emission profiles and secondary organic aerosol formation. We report here continued developments in the capabilities of our TAG system. Most recently, we have incorporated a two-dimensional chromatography (GC×GC) capability into TAG, and now have that instrument operating with a time of flight (TOF) MS detector. Two-dimensional chromatography provides two types of compound separation, most typically by volatility and polarity. It uses two columns with different stationary phases connected in series separated by a modulator. The modulator periodically traps analytes eluting from the first column, and injects fractions of this effluent onto the second column in the form of narrow pulses providing additional separation for co-eluting peaks. The approach

  4. Selenium speciation in flue desulfurization residues.

    PubMed

    Zhong, Liping; Cao, Yan; Li, Wenying; Xie, Kechang; Pan, Wei-Ping

    2011-01-01

    Flue gas from coal combustion contains significant amounts of volatile selenium (Se). The capture of Se in the flue gas desulfurization (FGD) scrubber unit has resulted in a generation of metal-laden residues. It is important to determine Se speciation to understand the environmental impact of its disposal. A simple method has been developed for selective inorganic Se(IV), Se(VI) and organic Se determination in the liquid-phase FGD residues by hydride generation atomic fluorescence spectrometry (AFS). It has been determined that Se(IV), Se(VI) and organic Se can be accurately determined with detection limits (DL) of 0.05, 0.06 and 0.06 microg/L, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1632c, and also by analyzing spiked tap-water samples. Analysis indicates that the concentration of Se is high in FGD liquid residues and primarily exists in a reduced state as selenite (Se(IV)). The toxicity of Se(IV) is the strongest of all Se species. Flue gas desulfurization residues pose a serious environmental risk.

  5. Speciation and phylogeography of giant petrels Macronectes.

    PubMed

    Techow, N M S M; O'Ryan, C; Phillips, R A; Gales, R; Marin, M; Patterson-Fraser, D; Quintana, F; Ritz, M S; Thompson, D R; Wanless, R M; Weimerskirch, H; Ryan, P G

    2010-02-01

    We examine global phylogeography of the two forms of giant petrel Macronectes spp. Although previously considered to be a single taxon, and despite debate over the status of some populations and the existence of minimal genetic data (one mitochondrial cytochrome b sequence per form), the current consensus based on morphology is that there are two species, Northern Giant Petrel M. halli and Southern Giant Petrel M. giganteus. This study examined genetic variation at cytochrome b as well as six microsatellite loci in giant petrels from 22 islands, representing most island groups at which the two species breed. Both markers support separate species status, although sequence divergence in cytochrome b was only 0.42% (corrected). Divergence was estimated to have occurred approximately 0.2mya, but with some colonies apparently separated for longer (up to 0.5 my). Three clades were found within giant petrels, which separated approximately 0.7mya, with the Southern Giant Petrel paraphyletic to a monophyletic Northern Giant Petrel. There was evidence of past fragmentation during the Pleistocene, with subsequent secondary contact within Southern Giant Petrels. The analysis also suggested a period of past population expansion that corresponded roughly to the timing of speciation and the separation of an ancestral giant petrel population from the fulmar Fulmarus clade. PMID:19755164

  6. Geographically multifarious phenotypic divergence during speciation

    PubMed Central

    Gompert, Zachariah; Lucas, Lauren K; Nice, Chris C; Fordyce, James A; Alex Buerkle, C; Forister, Matthew L

    2013-01-01

    Speciation is an important evolutionary process that occurs when barriers to gene flow evolve between previously panmictic populations. Although individual barriers to gene flow have been studied extensively, we know relatively little regarding the number of barriers that isolate species or whether these barriers are polymorphic within species. Herein, we use a series of field and lab experiments to quantify phenotypic divergence and identify possible barriers to gene flow between the butterfly species Lycaeides idas and Lycaeides melissa. We found evidence that L. idas and L. melissa have diverged along multiple phenotypic axes. Specifically, we identified major phenotypic differences in female oviposition preference and diapause initiation, and more moderate divergence in mate preference. Multiple phenotypic differences might operate as barriers to gene flow, as shown by correlations between genetic distance and phenotypic divergence and patterns of phenotypic variation in admixed Lycaeides populations. Although some of these traits differed primarily between species (e.g., diapause initiation), several traits also varied among conspecific populations (e.g., male mate preference and oviposition preference). PMID:23532669

  7. Gene transfer in bacteria: speciation without species?

    PubMed

    Lawrence, Jeffrey G

    2002-06-01

    Although Bacteria and Archaea reproduce by binary fission, exchange of genes among lineages has shaped the diversity of their populations and the diversification of their lineages. Gene exchange can occur by two distinct routes, each differentially impacting the recipient genome. First, homologous recombination mediates the exchange of DNA between closely related individuals (those whose sequences are sufficient similarly to allow efficient integration). As a result, homologous recombination mediates the dispersal of advantageous alleles that may rise to high frequency among genetically related individuals via periodic selection events. Second, lateral gene transfer can introduce novel DNA into a genome from completely unrelated lineages via illegitimate recombination. Gene exchange by this route serves to distribute genes throughout distantly related clades and therefore may confer complex abilities--not otherwise found among closely related lineages--onto the recipient organisms. These two mechanisms of gene exchange play complementary roles in the diversification of microbial populations into independent, ecologically distinct lineages. Although the delineation of microbial "species" then becomes difficult--if not impossible--to achieve, a cogent process of speciation can be predicted.

  8. Organotin speciation in Bizerte lagoon (Tunisia).

    PubMed

    Mzoughi, N; Lespes, G; Bravo, M; Dachraoui, M; Potin-Gautier, M

    2005-10-15

    For the first time, organotins have been assessed in samples collected from Bizerte lagoon, in Tunisia, during two seasons (summer and winter). The organotin distribution was studied in marine sediments and mussels tissues of this lagoon. Butyl-, phenyl- and octyltins were determined using a rapid speciation analytical method based on one-step ethylation/extraction with sodium tetraethylborate in aqueous phase. Simultaneously to the ethylation, the extraction was performed by either liquid/liquid extraction (LLE) or head-space solid phase microextraction (HS-SPME). Gas chromatography with pulsed flame photometric detection (GC-PFPD) was used to perform quantitative determination. The technique has been validated using biological and sediment reference materials. The different samples from Bizerte lagoon were found to be moderately contaminated, especially by butyltins. This pollution was attributed to industrial activities, which are very important in this area. Organotins appeared accumulated in both sediments and mussels, while significant degradations of triorganotins to monosubstituted ones was observed in water. PMID:16198682

  9. Mercury speciation and selenium in toothed-whale muscles.

    PubMed

    Sakamoto, Mineshi; Itai, Takaaki; Yasutake, Akira; Iwasaki, Toshihide; Yasunaga, Genta; Fujise, Yoshihiro; Nakamura, Masaaki; Murata, Katsuyuki; Chan, Hing Man; Domingo, José L; Marumoto, Masumi

    2015-11-01

    Mercury accumulates at high levels in marine mammal tissues. However, its speciation is poorly understood. The main goal of this investigation was to establish the relationships among mercury species and selenium (Se) concentrations in toothed-whale muscles at different mercury levels. The concentrations of total mercury (T-Hg), methylmercury (MeHg), inorganic mercury (I-Hg) and Se were determined in the muscles of four toothed-whale species: bottlenose dolphins (n=31), Risso's dolphins (n=30), striped dolphins (n=29), and short-finned pilot whales (n=30). In each species, the MeHg concentration increased with increasing T-Hg concentration, tending to reach a plateau. In contrast, the proportion of MeHg in T-Hg decreased from 90-100% to 20-40%. The levels of T-Hg and Se showed strong positive correlations. Se/I-Hg molar ratios rapidly decreased with the increase of I-Hg and reached almost 1 in all species. These results suggested that the demethylated MeHg immediately formed Se/I-Hg equimolar complex of mercury selenide (HgSe) in their muscles. In addition, an X-ray absorption fine structure analysis (XAFS) of a bottlenose dolphin muscle confirmed that the dominant chemical form of the Se/I-Hg equimolar complex was HgSe. HgSe was mainly localized in cells near the endomysium using electron probe microanalysis (EPMA). These results suggested that the demethylated MeHg finally deposits within muscle cells of bottlenose dolphin as an inert HgSe.

  10. Systemic distribution and speciation of diphenylarsinic acid fed to rats

    SciTech Connect

    Naranmandura, Hua Suzuki, Noriyuki; Takano, Juniti; McKnight-Whitford, Tony; Ogra, Yasumitsu; Suzuki, Kazuo T.; Le, X. Chris

    2009-06-01

    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 single 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.

  11. Sorption and Redox Speciation of Plutonium at the Illite Surface.

    PubMed

    Banik, Nidhu Lal; Marsac, Rémi; Lützenkirchen, Johannes; Diascorn, Alexandre; Bender, Kerstin; Marquardt, Christian Michael; Geckeis, Horst

    2016-02-16

    The geochemical behavior of Pu strongly depends on its redox speciation. In this study, we investigated Pu sorption onto Na-illite, a relevant component of potential host rocks for high-level nuclear waste repositories, under anaerobic conditions. When contacting Pu (85% Pu(IV), 11% Pu(V), and 4% Pu(III); 8 × 10(-11) < [Pu]tot/M < 10(-8)) with illite in 0.1 M NaCl at pH between 3 and 10, Pu uptake was characterized by log Rd > 4 (Rd: distribution coefficient in L kg(-1)). Small amounts of aqueous Pu(V) were detected in solution on contact with illite after 1 week, which is not expected to be stable at the measured redox potentials (Eh) in our experiments. This observation suggests time-dependent reduction of Pu(V) to Pu(IV). After one year, log Rd values had increased compared to those after 1 week due to the reduction of weakly adsorbing Pu(V). For pH < 5, Pu(IV) and Pu(III) coexisted in solution under our experimental conditions, showing that Pu(IV) reduction to Pu(III) occurred in the illite suspension. Taking (i) surface complexation constants determined for Eu(III)-illite interaction (with redox-insensitive Eu(III) as a chemical analogue to Pu(III)), (ii) the known constant for Pu(III)-Pu(IV) redox transition, and (iii) measured Eh and pH, overall Pu uptake was well-predicted. PMID:26793996

  12. Antimony uptake, efflux and speciation in arsenic hyperaccumulator Pteris vittata.

    PubMed

    Tisarum, Rujira; Lessl, Jason T; Dong, Xiaoling; de Oliveira, Letuzia M; Rathinasabapathi, Bala; Ma, Lena Q

    2014-03-01

    Even though antimony (Sb) and arsenic (As) are chemical analogs, differences exist on how they are taken up and translocated in plants. We investigated 1) Sb uptake, efflux and speciation in arsenic hyperaccumulator Pteris vittata after 1 d exposure to 1.6 or 8 mg/L antimonite (SbIII) or antimonate (SbV), 2) Sb uptake by PV accessions from Florida, China, and Brazil after 7 d exposure to 8 mg/L SbIII, and 3) Sb uptake and oxidation by excised PV fronds after 1 d exposure to 8 mg/L SbIII or SbV. After 1 d exposure, P. vittata took 23-32 times more SbIII than SbV, with all Sb being accumulated in the roots with the highest at 4,192 mg/kg. When exposed to 8 mg/L SbV, 98% of Sb existed as SbV in the roots. In comparison, when exposed to 8 mg/L SbIII, 81% of the total Sb remained as SbIII and 26% of the total Sb was effluxed out into the media. The three PV accessions had a similar ability to accumulate Sb at 12,000 mg/kg in the roots, with >99% of total Sb in the roots. Excised PV fronds translocated SbV more efficiently from the petioles to pinnae than SbIII and were unable to oxidize SbIII. Overall, P. vittata displayed efficient root uptake and efflux of SbIII with limited ability to translocate and transform in the roots.

  13. Speciation of phosphorus in the continental shelf sediments in the Eastern Arabian Sea

    NASA Astrophysics Data System (ADS)

    Acharya, Shiba Shankar; Panigrahi, Mruganka Kumar; Kurian, John; Gupta, Anil Kumar; Tripathy, Subhasish

    2016-03-01

    The distributions of various forms of phosphorus (P) and their relation with sediment geochemistry in two core sediments near Karwar and Mangalore offshore have been studied through the modified SEDEX procedure (Ruttenberg et al., 2009) and bulk chemical analysis. The present study provides the first quantitative analysis of complete phosphorus speciation in the core sediments of the Eastern Arabian shelf. The chemical index of alteration (CIA), chemical Index of Weathering (CIW) and Al-Ti-Zr ternary diagram suggest low to moderate source area weathering of granodioritic to tonalitic source rock composition, despite the intense orographic rainfall in the source area. Due to the presence of same source rock and identical oxic depositional environment, the studied sediments show the same range of variation of total phosphorus (24 to 83 μmol/g) with a down-depth depleting trend. Organic bound P and detrital P are the two major chemical forms followed by iron-bound P, exchangeable/loosely bound P and authigenic P. The authigenic P content in the sediments near Mangalore coast varies linearly with calcium (r=0.88) unlike that of Karwar coast. The different reactive-phosphorus pools exhibit identical depleting trend with depth. This indicates that the phosphorus released from the organic matter and Fe bound fractions are prevented from precipitating as authigenic phosphates in the deeper parts of the sediment column. The low concentration of total P, dominance of detrital non-reactive fraction of P and inhibition of formation of authigenic phosphate result in the absence of active phosphatization in the Eastern Arabian Shelf in the studied region. High sedimentation rate (35-58 cm/kyr) and absence of winnowing effect appear to be the dominant factor controlling the P-speciation in the studied sediments.

  14. Temporal patterns in daily measurements of inorganic and organic speciated PM2.5 in Denver

    PubMed Central

    Dutton, Steven J.; Rajagopalan, Balaji; Vedal, Sverre; Hannigan, Michael P.

    2013-01-01

    Airborne particulate matter less than 2.5 μm in aerodynamic diameter (PM2.5) has been linked to a wide range of adverse health effects and as a result is currently regulated by the U.S. Environmental Protection Agency. PM2.5 originates from a multitude of sources and has heterogeneous physical and chemical characteristics. These features complicate the link between PM2.5 emission sources, ambient concentrations and health effects. The goal of the Denver Aerosol Sources and Health (DASH) study is to investigate associations between sources and health using daily measurements of speciated PM2.5 in Denver. The datxa set being collected for the DASH study will be the longest daily speciated PM2.5 data set of its kind covering 5.5 years of daily inorganic and organic speciated measurements. As of 2008, 4.5 years of bulk measurements (mass, inorganic ions and total carbon) and 1.5 years of organic molecular marker measurements have been completed. Several techniques were used to reveal long-term and short-term temporal patterns in the bulk species and the organic molecular marker species. All species showed a strong annual periodicity, but their monthly and seasonal behavior varied substantially. Weekly periodicities appear in many compound classes with the most significant weekday/weekend effect observed for elemental carbon, cholestanes, hopanes, select polycyclic aromatic hydrocarbons (PAHs), heavy n-alkanoic acids and methoxyphenols. Many of the observed patterns can be explained by meteorology or anthropogenic activity patterns while others do not appear to have such obvious explanations. Similarities and differences in these findings compared to those reported from other cities are highlighted. PMID:23486844

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

    SciTech Connect

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

    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 P 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.

  16. Landslide-induced changes in soil phosphorus speciation and availability in Xitou, Central Taiwan

    NASA Astrophysics Data System (ADS)

    Cheng, Chih-Hsin; Hsiao, Sheng-Che; Huang, Yu-Sheng; Chen, Chiu-Ping; Menyailo, Oleg

    2016-04-01

    Phosphorus is an important nutrient in forest ecosystem. In tropical/subtropical areas, phosphorus is generally limited because of strong soil weathering but its speciation and availability can be changed by disturbances, such as the geological landslide events. In this study, we evaluated the changes in soil P speciation and availability after landslide in a mountainous forest ecosystem in Xitou, central Taiwan. Five soil pedons along a landslide/nonlanslide affected sequence from deep landslide deposit to nonlandslide were collected. The Hedley's sequential extraction procedure and synchrotron-based phosphorus x-ray adsorption near edge structure (XANES) spectroscopy were applied for the surface 0-10 cm and 10-20 cm soils to provide information concerning chemical and structural composition of phosphorus. The results indicated that plant available P (Resin-P + NaHCO3 extract P) and total P were reduced after landslide, from 150 and 500 mg kg-1, respectively, at nonlandsliding sites to 50 and 350 mg kg-1 at landsliding sites. However, the apatite-type P was significantly increased after landslide, from about 70 mg kg-1 at nonlandsliding sites to around 200 mg kg-1 at landsliding sites. Similar trend of enhanced apatite-type P after landslide was also observed in the XANES spectra. The ryegrass pot experiment confirmed that the landsliding soils were less fertile and had less growth rate. However, both nitrogen and phosphorus nutrients were limited at landsliding sites. The results demonstrated that soil P speciation and availability were significantly altered after landslide; these resultant changes are expected to influence functions in forest ecosystems.

  17. Changes in Zinc Speciation with Mine Tailings Acidification in a Semiarid Weathering Environment

    SciTech Connect

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

    2012-10-09

    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{sup -1}) and plant-available (590 to 75 mg kg{sup -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{sub 0.8}talc), Zn sorbed to ferrihydrite (Zn{sub adsFeOx}), and zinc sulfate (ZnSO{sub 4} {center_dot} 7H{sub 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{sub 2}O{sub 4}), hemimorphite (Zn{sub 4}Si{sub 2}O{sub 7}(OH){sub 2} {center_dot} H{sub 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.

  18. 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.

  19. Metal speciation in landfill leachates with a focus on the influence of organic matter

    SciTech Connect

    Claret, Francis; Tournassat, Christophe; Crouzet, Catherine; Gaucher, Eric C.; Schaefer, Thorsten; Braibant, Gilles; Guyonnet, Dominique

    2011-09-15

    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 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 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.

  20. 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

  1. The use of ion chromatography-D.C. plasma atomic emission spectrometry for the speciation of trace metals. Final performance technical report, February 1, 1995--January 31, 1998

    SciTech Connect

    Urasa, I.T.

    1998-06-12

    The chemistry of heavy metals in natural waters, industrial waste streams, and the environment is influenced by a number of factors including the prevailing matrix, their relative concentrations, and biologically or chemically induced transformations. Speciation, which entails the identification and quantification of all the forms of a metal or any other chemical entity present in a sample, is a necessary step in assessing the toxic and pollution effects and the overall impact of these entities on environmental systems. Analytical methods and protocols that can provide analytical data in the parts per billion concentration range and below are needed for these kinds of measurements. The thrust of this research was to develop metal speciation methods and techniques using direct current plasma (DCPAES) in combination with ion chromatography (IC), whereby the DCPAES serves as an element selective detector (ESD) for the metal species separated in the chromatographic column. While the metal speciation work carried out in this program has utilized the IC-DCPAES as the primary analytical measurement tool, other sample processing and preparation approaches have also been developed to enhance the effectiveness and capability of the chromatographic-element selective method of metal speciation. Post-column derivatization and solid phase extraction are two protocols which were incorporated with IC-ESD with significant improvements in the capability of the method.

  2. Female mate-choice behavior and sympatric speciation.

    PubMed

    Verzijden, Machteld N; Lachlan, Robert F; Servedio, Maria R

    2005-10-01

    Many models have investigated how the process of speciation may occur in sympatry. In these models, individuals are either asexual or mate choice is determined by very simple rules. Females, for example, may be assumed either to compare their phenotype to that of a potential mate, preferring to mate with similar males (phenotype matching), or to possess preference genes that determine which male phenotype they prefer. These rules often do not reflect the mate-choice rules found in empirical studies. In this paper, we compare these two modes of female choice with various types of sexual imprinting. We examine the efficacy of different mate-choice behavior in causing divergence in male traits under simple deterministic one-locus population genetic models as well as under polygenic, individual-based simulations based on the models of Dieckmann and Doebeli (1999). We find that the inheritance mechanism of mate choice can have a large effect on the ease of sympatric speciation. When females imprint on their mothers, the result of the model is similar to phenotype matching, where speciation can occur fairly easily. When females imprint on their fathers or imprint obliquely, speciation becomes considerably less likely. Finally, when females rely on preference genes, male trait evolution occurs easily, but the correlation between trait and preference can be weak, and interpreting these results as speciation may be suspect.

  3. Genomics of Rapid Incipient Speciation in Sympatric Threespine Stickleback

    PubMed Central

    Marques, David A.; Lucek, Kay; Meier, Joana I.; Mwaiko, Salome; Wagner, Catherine E.; Excoffier, Laurent; Seehausen, Ole

    2016-01-01

    Ecological speciation is the process by which reproductively isolated populations emerge as a consequence of divergent natural or ecologically-mediated sexual selection. Most genomic studies of ecological speciation have investigated allopatric populations, making it difficult to infer reproductive isolation. The few studies on sympatric ecotypes have focused on advanced stages of the speciation process after thousands of generations of divergence. As a consequence, we still do not know what genomic signatures of the early onset of ecological speciation look like. Here, we examined genomic differentiation among migratory lake and resident stream ecotypes of threespine stickleback reproducing in sympatry in one stream, and in parapatry in another stream. Importantly, these ecotypes started diverging less than 150 years ago. We obtained 34,756 SNPs with restriction-site associated DNA sequencing and identified genomic islands of differentiation using a Hidden Markov Model approach. Consistent with incipient ecological speciation, we found significant genomic differentiation between ecotypes both in sympatry and parapatry. Of 19 islands of differentiation resisting gene flow in sympatry, all were also differentiated in parapatry and were thus likely driven by divergent selection among habitats. These islands clustered in quantitative trait loci controlling divergent traits among the ecotypes, many of them concentrated in one region with low to intermediate recombination. Our findings suggest that adaptive genomic differentiation at many genetic loci can arise and persist in sympatry at the very early stage of ecotype divergence, and that the genomic architecture of adaptation may facilitate this. PMID:26925837

  4. Speciation with gene flow on Lord Howe Island

    PubMed Central

    Papadopulos, Alexander S. T.; Baker, William J.; Crayn, Darren; Butlin, Roger K.; Kynast, Ralf G.; Hutton, Ian; Savolainen, Vincent

    2011-01-01

    Understanding the processes underlying the origin of species is a fundamental goal of biology. It is widely accepted that speciation requires an interruption of gene flow between populations: ongoing gene exchange is considered a major hindrance to population divergence and, ultimately, to the evolution of new species. Where a geographic barrier to reproductive isolation is lacking, a biological mechanism for speciation is required to counterbalance the homogenizing effect of gene flow. Speciation with initially strong gene flow is thought to be extremely rare, and few convincing empirical examples have been published. However, using phylogenetic, karyological, and ecological data for the flora of a minute oceanic island (Lord Howe Island, LHI), we demonstrate that speciation with gene flow may, in fact, be frequent in some instances and could account for one in five of the endemic plant species of LHI. We present 11 potential instances of species divergence with gene flow, including an in situ radiation of five species of Coprosma (Rubiaceae, the coffee family). These results, together with the speciation of Howea palms on LHI, challenge current views on the origin of species diversity. PMID:21730151

  5. Sexual selection drives speciation in an Amazonian frog

    USGS Publications Warehouse

    Boul, K.E.; Funk, W.C.; Darst, C.R.; Cannatella, D.C.; Ryan, M.J.

    2007-01-01

    One proposed mechanism of speciation is divergent sexual selection, whereby divergence in female preferences and male signals results in behavioural isolation. Despite the appeal of this hypothesis, evidence for it remains inconclusive. Here, we present several lines of evidence that sexual selection is driving behavioural isolation and speciation among populations of an Amazonian frog (Physalaemus petersi). First, sexual selection has promoted divergence in male mating calls and female preferences for calls between neighbouring populations, resulting in strong behavioural isolation. Second, phylogenetic analysis indicates that populations have become fixed for alternative call types several times throughout the species' range, and coalescent analysis rejects genetic drift as a cause for this pattern, suggesting that this divergence is due to selection. Finally, gene flow estimated with microsatellite loci is an average of 30 times lower between populations with different call types than between populations separated by a similar geographical distance with the same call type, demonstrating genetic divergence and incipient speciation. Taken together, these data provide strong evidence that sexual selection is driving behavioural isolation and speciation, supporting sexual selection as a cause for speciation in the wild. ?? 2006 The Royal Society.

  6. On the origin of species by sympatric speciation

    NASA Astrophysics Data System (ADS)

    Dieckmann, Ulf; Doebeli, Michael

    1999-07-01

    Understanding speciation is a fundamental biological problem. It is believed that many species originated through allopatric divergence, where new species arise from geographically isolated populations of the same ancestral species. In contrast, the possibility of sympatric speciation (in which new species arise without geographical isolation) has often been dismissed, partly because of theoretical difficulties,. Most previous models analysing sympatric speciation concentrated on particular aspects of the problem while neglecting others. Here we present a model that integrates a novel combination of different features and show that sympatric speciation is a likely outcome of competition for resources. We use multilocus genetics to describe sexual reproduction in an individual-based model, and we consider the evolution of assortative mating (where individuals mate preferentially with like individuals) depending either on an ecological character affecting resource use or on a selectively neutral marker trait. In both cases, evolution of assortative mating often leads to reproductive isolation between ecologically diverging subpopulations. When assortative mating depends on a marker trait, and is therefore not directly linked to resource competition, speciation occurs when genetic drift breaks the linkage equilibrium between the marker and the ecological trait. Our theory conforms well with mounting empirical evidence for the sympatric origin of many species.

  7. Selective Separation and Determination of Heavy Metals (Cd, Pb, Cr) Speciation Forms from Hortic Antrosols

    NASA Astrophysics Data System (ADS)

    Bulgariu, D.; Bulgariu, L.

    2009-04-01

    The speciation, inter-phases distribution and biodisponibility of heavy metals in soils represent one of main problem of environmental geochemistry and agro-chemistry. This problem is very important in case of hortic antrosols (soils from glasshouses) for the elimination of agricultural products (fruits, vegetables) contamination with heavy metals. In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have bee performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation

  8. Neptunium redox speciation at the illite surface

    NASA Astrophysics Data System (ADS)

    Marsac, Rémi; Banik, Nidhu lal; Lützenkirchen, Johannes; Marquardt, Christian Michael; Dardenne, Kathy; Schild, Dieter; Rothe, Joerg; Diascorn, Alexandre; Kupcik, Tomas; Schäfer, Thorsten; Geckeis, Horst

    2015-03-01

    Neptunium (Np(V)) sorption onto a purified illite is investigated as a function of pH (3-10) and [NpVO2+]tot(3 × 10-8-3 × 10-4 M) in 0.1 M NaCl under Ar atmosphere. After about one week reaction time, only insignificant variation of Np sorption is observed and the establishment of reaction equilibrium can be assumed. Surprisingly, solid-liquid distribution ratios (Rd) are clearly higher than those measured for Np(V) sorption onto illite under aerobic conditions. The observation that Rd increases with decreasing pe (pe = -log ae-) suggests partial reduction to Np(IV), although measured redox potentials (pe values) at a first glance suggest the predominance of Np(V). Reduction to Np(IV) at the illite surface could indeed be confirmed by X-ray absorption near-edge spectroscopy (XANES). Np speciation in presence of the purified Na-illite under given conditions is consistently described by applying the 2 sites protolysis non-electrostatic surface complexation and cation exchange model. Measured pe data are taken to calculate Np redox state and surface complexation constants for Np(IV) are derived by applying a data fitting procedure. Constants are very consistent with results obtained by applying an existing linear free energy relationship (LFER). Taking Np(IV) surface complexation constants into account shifts the calculated Np(V)/Np(IV) redox borderline in presence of illite surfaces by 3-5 pe units (0.2-0.3 V) towards redox neutral conditions. Our study suggests that Np(V) reduction in presence of a sorbing mineral phase is thermodynamically favored.

  9. A speciation gene for left-right reversal in snails results in anti-predator adaptation.

    PubMed

    Hoso, Masaki; Kameda, Yuichi; Wu, Shu-Ping; Asami, Takahiro; Kato, Makoto; Hori, Michio

    2010-01-01

    How speciation genes can spread in a population is poorly understood. In land snails, a single gene for left-right reversal could be responsible for instant speciation, because dextral and sinistral snails have difficulty in mating. However, the traditional two-locus speciation model predicts that a mating disadvantage for the reversal should counteract this speciation. In this study, we show that specialized snake predation of the dextral majority drives prey speciation by reversal. Our experiments demonstrate that sinistral Satsuma snails (Stylommatophora: Camaenidae) survive predation by Pareas iwasakii (Colubroidea: Pareatidae). Worldwide biogeography reveals that stylommatophoran snail speciation by reversal has been accelerated in the range of pareatid snakes, especially in snails that gain stronger anti-snake defense and reproductive isolation from dextrals by sinistrality. Molecular phylogeny of Satsuma snails further provides intriguing evidence of repetitive speciation under snake predation. Our study demonstrates that a speciation gene can be fixed in populations by positive pleiotropic effects on survival.

  10. Mercury speciation in the colloidal fraction of a soil polluted by a chlor-alkali plant: a case study in the South of Italy.

    PubMed

    Santoro, A; Terzano, R; Blo, G; Fiore, S; Mangold, S; Ruggiero, P

    2010-03-01

    Mercury (Hg) speciation in different size fractions of a soil sample collected near an industrial area located in the South of Italy, which had been polluted by the dumping of Hg-containing wastes from a chlor-alkali plant, was investigated by XANES spectroscopy. In particular, a special procedure has been developed to study the soil colloidal fraction, both for sample preparation and for XANES data collection. In this soil, Hg was speciated in quite insoluble inorganic forms such as cinnabar (alpha-HgS), metacinnabar (beta-HgS), corderoite (Hg(3)S(2)Cl(2)), and some amorphous Hg, S and Cl-containing species, all derived from the land-disposal of K106 Hg-containing wastes. The contribution of the above-mentioned chemical forms to Hg speciation changed as a function of particle size. For the fraction <2 mm the speciation was: amorphous Hg-S-Cl (34%) > corderoite (26%) > cinnabar (20%) = metacinnabar (20%); for the fraction <2 microm: amorphous Hg-S-Cl (40%) > metacinnabar (24%) > corderoite (20%) > cinnabar (16%); and for the fraction 430-650 nm, where most of the colloidal Hg was concentrated: amorphous Hg-S-Cl (56%) > metacinnabar (33%) > corderoite (6%) > cinnabar (5%). From these data it emerged that, even if Hg was speciated in quite insoluble forms, the colloidal fraction, which is the most mobile and thus the most dangerous, was enriched in relatively more soluble species (i.e. amorphous Hg-S-Cl and metacinnabar), as compared with cinnabar. This aspect should be seriously taken into account when planning environmental risk assessment, since the small particle size in which Hg is concentrated and the changing speciation passing from millimetre to nanometre size could turn apparently safe conditions into more hazardous ones. PMID:20157270

  11. Rapid acceleration of plant speciation during the Anthropocene.

    PubMed

    Thomas, Chris D

    2015-08-01

    Speciation rates need to be considered when estimating human impacts on the numbers of species on Earth, given that past mass extinctions have been followed by the accelerated origination of new taxa. Here, I suggest that the Anthropocene is already exhibiting a greatly accelerated plant speciation rate due to agriculture, horticulture, and the human-mediated transport of species, followed by hybridisation. For example, more new plant species have come into existence in Europe over the past three centuries than have been documented as becoming extinct over the same period, even though most new hybrid-origin species are likely to remain undetected. Current speciation rates are unusually high and they could be higher than during or after previous mass extinctions.

  12. Rapid acceleration of plant speciation during the Anthropocene.

    PubMed

    Thomas, Chris D

    2015-08-01

    Speciation rates need to be considered when estimating human impacts on the numbers of species on Earth, given that past mass extinctions have been followed by the accelerated origination of new taxa. Here, I suggest that the Anthropocene is already exhibiting a greatly accelerated plant speciation rate due to agriculture, horticulture, and the human-mediated transport of species, followed by hybridisation. For example, more new plant species have come into existence in Europe over the past three centuries than have been documented as becoming extinct over the same period, even though most new hybrid-origin species are likely to remain undetected. Current speciation rates are unusually high and they could be higher than during or after previous mass extinctions. PMID:26115931

  13. Computer simulations of sympatric speciation in a simple food web.

    PubMed

    Luz-Burgoa, K; Dell, Tony; de Oliveira, S Moss

    2005-07-01

    Galapagos finches, have motivated much theoretical research aimed at understanding the processes associated with the formation of the species. Inspired by them, in this paper we investigate the process of sympatric speciation in a simple food web model. For that we modify the individual-based Penna model that has been widely used to study aging as well as other evolutionary processes. Initially, our web consists of a primary food source and a single herbivore species that feeds on this resource. Subsequently we introduce a predator that feeds on the herbivore. In both instances we manipulate directly a basal resource distribution and monitor the changes in the populations. Sympatric speciation is obtained for the top species in both cases, and our results suggest that the speciation velocity depends on how far up, in the food chain, the focus population is feeding. Simulations are done with three different sexual imprinting-like mechanisms, in order to discuss adaptation by natural selection.

  14. Plutonium Speciation in Support of Oxidative-Leaching Demonstration Test

    SciTech Connect

    Sinkov, Sergey I.

    2007-10-31

    Bechtel National, Inc. (BNI) is evaluating the plutonium speciation in caustic solutions that reasonably represent the process streams from the oxidative-leaching demonstration test. Battelle—Pacific Northwest Division (PNWD) was contracted to develop a spectrophotometric method to measure plutonium speciation at submicromolar (< 10-6 M) concentrations in alkaline solutions in the presence of chromate and carbonate. Data obtained from the testing will be used to identify the oxidation state of Pu(IV), Pu(V), and Pu(VI) species, which potentially could exist in caustic leachates. Work was initially conducted under contract number 24590-101-TSA-W000-00004 satisfying the needs defined in Appendix C of the Research and Technology Plan TSS A-219 to evaluate the speciation of chromium, plutonium, and manganese before and after oxidative leaching. In February 2007, the contract mechanism was switched to Pacific Northwest National Laboratory (PNNL) Operating Contract MOA: 24590-QL-HC9-WA49-00001.

  15. Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite.

    PubMed

    Voegelin, Andreas; Jacquat, Olivier; Pfister, Sabina; Barmettler, Kurt; Scheinost, Andreas C; Kretzschmar, Ruben

    2011-01-01

    The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn

  16. Possible incipient sympatric ecological speciation in blind mole rats (Spalax).

    PubMed

    Hadid, Yarin; Tzur, Shay; Pavlícek, Tomáš; Šumbera, Radim; Šklíba, Jan; Lövy, Matěj; Fragman-Sapir, Ori; Beiles, Avigdor; Arieli, Ran; Raz, Shmuel; Nevo, Eviatar

    2013-02-12

    Sympatric speciation has been controversial since it was first proposed as a mode of speciation. Subterranean blind mole rats (Spalacidae) are considered to speciate allopatrically or peripatrically. Here, we report a possible incipient sympatric adaptive ecological speciation in Spalax galili (2n = 52). The study microsite (0.04 km(2)) is sharply subdivided geologically, edaphically, and ecologically into abutting barrier-free ecologies divergent in rock, soil, and vegetation types. The Pleistocene Alma basalt abuts the Cretaceous Senonian Kerem Ben Zimra chalk. Only 28% of 112 plant species were shared between the soils. We examined mitochondrial DNA in the control region and ATP6 in 28 mole rats from basalt and in 14 from chalk habitats. We also sequenced the complete mtDNA (16,423 bp) of four animals, two from each soil type. Remarkably, the frequency of all major haplotype clusters (HC) was highly soil-biased. HCI and HCII are chalk biased. HC-III was abundant in basalt (36%) but absent in chalk; HC-IV was prevalent in basalt (46.5%) but was low (20%) in chalk. Up to 40% of the mtDNA diversity was edaphically dependent, suggesting constrained gene flow. We identified a homologous recombinant mtDNA in the basalt/chalk studied area. Phenotypically significant divergences differentiate the two populations, inhabiting different soils, in adaptive oxygen consumption and in the amount of outside-nest activity. This identification of a possible incipient sympatric adaptive ecological speciation caused by natural selection indirectly refutes the allopatric alternative. Sympatric ecological speciation may be more prevalent in nature because of abundant and sharply abutting divergent ecologies.

  17. Application of the Rietveld method to assess chromium(VI) speciation in chromite ore processing residue.

    PubMed

    Chrysochoou, Maria; Dermatas, Dimitris

    2007-03-15

    The Rietveld method allows the quantification of crystalline phases and amorphous material identified by X-ray powder diffraction (XRPD) and other diffraction methods. The method assists in determining the speciation of contaminants in solid matrices both qualitatively and quantitatively in a statistically defensible approach, as it does not focus on a microscale. Rietveld was applied to chromite ore processing residue (COPR), a cementitious waste containing hexavalent chromium. Calcium aluminum chromium oxide hydrates (CACs) were the crystalline phases identified by XRPD that bind Cr(6+) in COPR according to their chemical formula. Rietveld quantification, combined with mass balances on Cr(6+), showed that CACs may bind Cr(6+) in variable percentages, ranging from 25% to 85%. Analysis of duplicate samples showed that material variability is the predominant factor of uncertainty in evaluating the role of CACs in Cr(6+) speciation, provided that a consistent quantification strategy is pursued. The choice of strategy was performed on the basis of the pertinent literature, preliminary analyses of the equipment and the software settings, and mass balances. The correlation between the average CAC-bound Cr(6+) concentration and the total Cr(6+) for five samples (R(2)=0.94), extracted from different zones and soil borings, suggests that CACs are a primary sink for Cr(6+) in COPR. PMID:16842911

  18. Changes of Cu, Zn, and Cd speciation in sewage sludge during connposting.

    PubMed

    Gao, Ding; Zheng, Guo-di; Chen, Tong-bin; Luo, Wei; Gao, Wei; Zhang, Yi-an; Li, Yan-xia

    2005-01-01

    The potential toxicity risks from heavy metals depend on their chemical speciation. The four stages of the Tessier sequential extraction method were employed to investigate changes in heavy metal speciation (Cu, Zn, and Cd) of sewage sludge during forced aeration composting, and then to identify whether the composting process would reduce or enhance their toxicities. Throughout the composting process, the exchangeable, carbonate-bound, Fe-Mn oxide-bound, and organic matter-bound fractions of Cu were converted to the residual Cu fraction. The organic matter-bound Cu fraction greatly contributed to this transformation. Residual Zn fraction was transformed to the Fe-Mn oxide-bound and organic matter-bound fractions after composting. The residual Zn fraction was a major contributor to the organic matter-bound Zn fraction. The availability of Cu and Zn was reduced by composting such that the risk of heavy metal toxicity decreased with prolonged treatment times. Additionally, attention should be paid to the increased availability of Cd in sewage sludge after composting treatment.

  19. [Influence of Dissimilatory Iron Reduction on the Speciation and Bioavailability of Heavy Metals in Soil].

    PubMed

    Si, You-bin; Wang, Juan

    2015-09-01

    Fe(III) dissimilatory reduction by microbes is an important process of producing energy in the oxidation of organic compounds under anaerobic condition with Fe(III) as the terminal electron acceptor and Fe(II) as the reduction product. This process is of great significance in element biogeochemical cycle. Iron respiration has been described as one of the most ancient forms of microbial metabolism on the earth, which is bound up with material cycle in water, soil and sediments. Dissimilatory iron reduction plays important roles in heavy metal form transformation and the remediation of heavy metal and radionuclide contaminated soils. In this paper, we summarized the research progress of iron reduction in the natural environment, and discussed the influence and the mechanism of dissimilatory iron reduction on the speciation and bioavailability of heavy metals in soil. The effects of dissimilatory iron reduction on the speciation of heavy metals may be attributed to oxidation and reduction, methytation and immobilization of heavy metals in relation to their bioavailability in soils. The mechanisms of Fe(III) dissimilatory reduction on heavy metal form transformation contain biological and chemical interactions, but the mode of interaction remains to be further investigated. PMID:26717720

  20. Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques.

    PubMed

    Terzano, Roberto; Santoro, Anna; Spagnuolo, Matteo; Vekemans, Bart; Medici, Luca; Janssens, Koen; Göttlicher, Jörg; Denecke, Melissa A; Mangold, Stefan; Ruggiero, Pacifico

    2010-08-01

    Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg(-1). Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as mu-XRF, mu-XRD and mu-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 microm. The main Hg-species found in the soil samples were metacinnabar (beta-HgS), cinnabar (alpha-HgS), corderoite (Hg(3)S(2)Cl(2)), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 microm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution. PMID:20605298

  1. Effects of a reservoir flushing on trace metal partitioning, speciation and benthic invertebrates in the floodplain.

    PubMed

    Peter, Dorothea Hug; Castella, Emmanuel; Slaveykova, Vera I

    2014-12-01

    Elimination of sediments from river reservoirs is a common management problem for hydroelectric power plants. Periodical flushing can have negative impacts downstream. This study investigated the impact of a flushing event on the physico-chemical changes in the downstream sections and on the consequences for the benthic macroinvertebrate community. A special emphasis was placed on trace metal fate, partitioning and speciation. The assessment of taxonomic diversity and the frequency of taxa with specific traits was used to estimate the impact on the macroinvertebrate community. Trace metals were measured in the dissolved and particulate fraction, in the surface sediment and in selected macroinvertebrates. Bioanalogical diffusive gradient thin films (DGT) complemented the approach. The results showed an increase of Al, Co, Mn and Ni in the dissolved fraction (Mdis). Crdis, Fedis, Pbdis, and Cudis showed strong spatial variation. In the exchangeable fraction of particulate metals, trends were contrasted, depending on the metal. The calculated free ion and DGT concentrations increased during the flush for all metals, except for Cu. Accumulation in invertebrates increased only in a small number of cases. Macroinvertebrate diversity was negatively impacted as shown by lower taxonomic richness and rarefied richness after the event. Trait profiles were also affected. Overall, the study revealed that flushing operations have an impact on trace metal partitioning between dissolved, suspended particulate matter and sediments, metal speciation, as well as the functional invertebrate diversity.

  2. Detailed Characterization and Profiles of Crankcase and Diesel Particular Matter Exhaust Emissions Using Speciated Organics

    PubMed Central

    Zielinska, Barbara; Campbell, David; Lawson, Douglas R.; Ireson, Robert G.; Weaver, Christopher S.; Hesterberg, Thomas W.; Larson, Timothy; Davey, Mark; Liu, L.-J. Sally

    2008-01-01

    A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as intentional quantitative tracers for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes, and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 μg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions. PMID:18754490

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

    PubMed Central

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

    2015-01-01

    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. PMID:26574673

  4. 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

    2014-09-01

    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. PMID:25126837

  5. [Influence of Dissimilatory Iron Reduction on the Speciation and Bioavailability of Heavy Metals in Soil].

    PubMed

    Si, You-bin; Wang, Juan

    2015-09-01

    Fe(III) dissimilatory reduction by microbes is an important process of producing energy in the oxidation of organic compounds under anaerobic condition with Fe(III) as the terminal electron acceptor and Fe(II) as the reduction product. This process is of great significance in element biogeochemical cycle. Iron respiration has been described as one of the most ancient forms of microbial metabolism on the earth, which is bound up with material cycle in water, soil and sediments. Dissimilatory iron reduction plays important roles in heavy metal form transformation and the remediation of heavy metal and radionuclide contaminated soils. In this paper, we summarized the research progress of iron reduction in the natural environment, and discussed the influence and the mechanism of dissimilatory iron reduction on the speciation and bioavailability of heavy metals in soil. The effects of dissimilatory iron reduction on the speciation of heavy metals may be attributed to oxidation and reduction, methytation and immobilization of heavy metals in relation to their bioavailability in soils. The mechanisms of Fe(III) dissimilatory reduction on heavy metal form transformation contain biological and chemical interactions, but the mode of interaction remains to be further investigated.

  6. 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

    2014-09-01

    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.

  7. 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.

  8. Sulfur speciation in heavy petroleums: Information from X-ray absorption near-edge structure

    NASA Astrophysics Data System (ADS)

    Waldo, Geoffrey S.; Carlson, Robert M. K.; Moldowan, J. Michael; Peters, Kenneth E.; Penner-hahn, James E.

    1991-03-01

    The chemical speciation of sulfur in heavy petroleums, petroleum source rock extracts, and source rock pyrolysis products was studied using X-ray absorption near-edge structure (XANES) spectroscopy. The good energy resolution (ca. 0.5 eV) at the sulfur K edge and the strong dependence of XANES on the sulfur environment combine to give excellent sensitivity to changes in the electronic and structural environment of the sulfur. This has permitted identification and approximate quantitation of different classes of sulfur-containing compounds (e.g., sulfur, sulfides (including disulfides and polysulfides as a group), thiophenes, sulfoxides, sulfones, sulfinic acids, sulfonic acids, and sulfate) in a series of petroleums and petroleum source rocks. Our results indicate that the sulfur speciation of geological samples can be correlated with differences in source depositional environment, thermal maturity, and aromaticity. We report organosulfur compositions for the asphaltene, maltene, and liquid Chromatographie fractions of two sulfur-rich oils. In addition, we find that the organosulfur species in some, but not all, oils are subject to oxidation upon storage and thus may also be susceptible to oxidation in shallow reservoirs exposed to oxic waters. This work illustrates the utility of XANES as a direct spectroscopic probe for the quantitative determination of sulfur species in geological samples.

  9. 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...

  10. XANES Identification of Plutonium Speciation in RFETS Samples

    SciTech Connect

    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.

  11. Cesium Speciation in Dust from Municipal Solid Waste and Sewage Sludge Incineration by Synchrotron Radiation Micro-X-ray Analysis.

    PubMed

    Shiota, Kenji; Takaoka, Masaki; Fujimori, Takashi; Oshita, Kazuyuki; Terada, Yasuko

    2015-11-17

    The chemical behavior of Cs in waste incineration processes is important to consider when disposing of radionuclide-contaminated waste from the Fukushima Daiichi nuclear power plant accident in Japan. To determine the speciation of Cs, we attempted the direct speciation of trace amounts of stable Cs in the dust from municipal solid waste incineration (MSWI) and sewage sludge incineration (SSI) by micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption fine structure (μ-XAFS) at the SPring-8 facility. The μ-XRF results revealed that locally produced Cs was present in MSWI and SSI dust within the cluster size range of 2-10 μm. The μ-XAFS analysis confirmed that the speciation of Cs in MSWI dust was similar to that of CsCl, while in SSI dusts it was similar to pollucite. The solubility of Cs was considered to be influenced by the exact Cs species present in incineration residue.

  12. Chromium and its speciation in water samples by HPLC/ICP-MS--technique establishing metrological traceability: a review since 2000.

    PubMed

    Markiewicz, Barbara; Komorowicz, Izabela; Sajnóg, Adam; Belter, Magdalena; Barałkiewicz, Danuta

    2015-01-01

    Chromium holds a special position among living organisms because depending on its species it can be either essential or toxic. Cr(VI) even at very low concentrations is harmful and carcinogenic, while Cr(III) is a necessary microelement for cellular metabolism. Therefore, a simple analysis of Cr concentration in collected samples will not be able to distinguish these differences effectively: for a proper chemical analysis we need to perform a reliable detection and quantification of Cr species. Separation and detection of chromium can be accomplished with high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS) in a one-step. Our review assembles articles published since 2000 regarding chromium speciation in water samples with the use of HPLC/ICP-MS. It addresses the following issues: chromium chemistry, the possibilities of dealing with interferences, metrological aspects, analytical performance and speciated isotope dilution mass spectrometry (SIDMS) which is a definitive measurement method. The authors would like to advocate this hyphenated advanced technique as well as the metrological approach in speciation analysis of chromium.

  13. Cesium Speciation in Dust from Municipal Solid Waste and Sewage Sludge Incineration by Synchrotron Radiation Micro-X-ray Analysis.

    PubMed

    Shiota, Kenji; Takaoka, Masaki; Fujimori, Takashi; Oshita, Kazuyuki; Terada, Yasuko

    2015-11-17

    The chemical behavior of Cs in waste incineration processes is important to consider when disposing of radionuclide-contaminated waste from the Fukushima Daiichi nuclear power plant accident in Japan. To determine the speciation of Cs, we attempted the direct speciation of trace amounts of stable Cs in the dust from municipal solid waste incineration (MSWI) and sewage sludge incineration (SSI) by micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption fine structure (μ-XAFS) at the SPring-8 facility. The μ-XRF results revealed that locally produced Cs was present in MSWI and SSI dust within the cluster size range of 2-10 μm. The μ-XAFS analysis confirmed that the speciation of Cs in MSWI dust was similar to that of CsCl, while in SSI dusts it was similar to pollucite. The solubility of Cs was considered to be influenced by the exact Cs species present in incineration residue. PMID:26477930

  14. Major and trace-element speciation in deep-sea hydrothermal plumes of Eastern Lau Spreading Center

    NASA Astrophysics Data System (ADS)

    Sorensen, J. V.; Toner, B.; Dick, G.; Breier, J. A.; Jiang, H.

    2011-12-01

    Hydrothermal venting at mid-ocean ridge systems results in the flux of heat and chemical species from the crust to the cold, oxic waters of the deep ocean. The mixing of these fluids creates a buoyant, rising plume with dynamic biogeochemical processes and rapid physical mixing. The global distribution of these vent systems makes hydrothermal plumes an important source and sink of biogeochemically active elements to ocean basins. The goal of this study is to characterize the transport and fate of the chemical species within individual hydrothermal plumes. By doing so, we hope to understand the interrelationship of physical-chemical gradients present in plumes with trace element uptake by plume particles. To achieve this goal a field study was undertaken at the Eastern Lau Spreading Center (ELSC). The larger study will include analysis of all sites, however here we report the geochemical and trace-element speciation of a single buoyant plume within ABE vent field. A series of replicate sample sets were collected by in situ filtration at 0.5m, 40m, 200m within a buoyant plume using the ROV JASON. Above plume background and near bottom background sample sets were also collected. Hydrothermal plume particles in sample replicates have been analysed for bulk geochemistry, chemical speciation, and particle-by-particle mineralogy. The speciation of iron, a major particle forming element, and the distribution of select trace elements (arsenic, vanadium) is described using chemical mapping, X-ray absorption spectroscopy, and X-ray diffraction. Particle morphology and carbon speciation are described using scanning transmission X-ray microscopy (STXM). This data is being integrated into a physical-geochemical model, and will be used to estimate the energy available to chemlithoautotrophic organisms in plumes. The distribution of minerals and incorporated trace elements (e.g. arsenic) will be used to interpret uptake mechanisms. The research will help us understand processes

  15. Room Temperature Cation Exchange Reaction in Nanocrystals for Ultrasensitive Speciation Analysis of Silver Ions and Silver Nanoparticles.

    PubMed

    Huang, Ke; Xu, Kailai; Tang, Jie; Yang, Lu; Zhou, Jingrong; Hou, Xiandeng; Zheng, Chengbin

    2015-07-01

    To evaluate the toxicity of silver nanoparticles (AgNPs) and Ag(+) and gain deep insight into the transformation of AgNPs in the environment or organisms, ultrasensitive analytical methods are needed for their speciation analysis. About 40-fold of Cd(2+) in CdTe ionic nanocrystals can be "bombarded-and-exploded" (exchanged) in less than 1 min simply by mixing the nanocrystals with Ag(+) solution at room temperature, while this cation exchange reaction did not occur when only silver nanoparticles were present. On the basis of this striking difference, an ultrasensitive method was developed for speciation analysis of Ag(+) and AgNPs in complex matrices. The released Cd(2+) was reduced to its volatile species by sodium tetrahydroborate, which was separated and swept to an inductively coupled plasma mass spectrometer (ICPMS) or an atomic fluorescence spectrometer (AFS) for the indirect but ultrasensitive detection of Ag(+). Owing to the remarkable signal amplification via the cation exchange reaction and the advantages of chemical vapor generation for sampling, the limit of detection was 0.0003 μg L(-1) for Ag(+) by ICPMS, which was improved by 100-fold compared to the conventional method. Relative standard deviations are better than 2.5% at a concentration of 0.5 μg L(-1) Ag(+) or AgNPs regardless of the detector. The proposed method retains several unique advantages, including ultrahigh sensitivity, speciation analysis, simplicity and being organic reagent-free, and has been successfully utilized for speciation analysis of Ag(+) and AgNPs in environmental water samples and paramecium cells. PMID:26017198

  16. Microscale characterization of sulfur speciation in lake sediments.

    PubMed

    Zeng, Teng; Arnold, William A; Toner, Brandy M

    2013-02-01

    Prairie pothole lakes (PPLs) are naturally sulfur-enriched wetlands in the glaciated prairie region of North America. High sulfate levels and dynamic hydrogeochemistry in combination render PPLs a unique environment to explore the speciation of sedimentary sulfur (S). The goals of this research were to define and quantify the solid-phase S pools in PPL sediments and track seasonal dynamics of S speciation. A quantitative X-ray microprobe method was developed based on S 1s X-ray absorption near-edge structure (XANES) spectroscopy and multienergy X-ray fluorescence mapping. Three S pools-pyritic S, reduced organic S (organic mono- and disulfide), and oxidized S (inorganic sulfate, ester sulfate, and sulfonate)-were identified in PPL sediments. No significant seasonal variation was evident for total S, but S speciation showed a seasonal response. During the spring-summer transition, the reduced organic S decreased from 55 to 15 mol %, with a concomitant rise in the oxidized S. During the summer-fall transition, the trend reversed and the reduced organic S grew to 75 mol % at the expense of the oxidized S. The pyritic S, on the other hand, remained relatively constant (∼22 mol %) over time. The seasonal changes in S speciation have strong potential to force the cycling of elements such as mercury in prairie wetlands.

  17. FINE PARTICULATE MATTER (PM) AND ORGANIC SPECIATION OF FIREPLACE EMISSIONS

    EPA Science Inventory

    This paper presents a summary of fireplace particle size and organic speciation data gathered to date in an on-going project. Tests are being conducted in a residential wood combustion (RWC) laboratory on three factory-built fireplaces. RWC wood smoke particles <10?m (PM10) con...

  18. Speciation dynamics and biogeography of Neotropical spiral gingers (Costaceae).

    PubMed

    André, Thiago; Salzman, Shayla; Wendt, Tânia; Specht, Chelsea D

    2016-10-01

    Species can arise via the divisive effects of allopatry as well as due to ecological and/or reproductive character displacement within sympatric populations. Two separate lineages of Costaceae are native to the Neotropics; an early-diverging clade endemic to South America (consisting of ca. 16 species in the genera Monocostus, Dimerocostus and Chamaecostus); and the Neotropical Costus clade (ca. 50 species), a diverse assemblage of understory herbs comprising nearly half of total familial species richness. We use a robust dated molecular phylogeny containing most of currently known species to inform macroevolutionary reconstructions, enabling us to examine the context of speciation in Neotropical lineages. Analyses of speciation rate revealed a significant variation among clades, with a rate shift at the most recent common ancestor of the Neotropical Costus clade. There is an overall predominance of allopatric speciation in the South American clade, as most species display little range overlap. In contrast, sympatry is much higher within the Neotropical Costus clade, independent of node age. Our results show that speciation dynamics during the history of Costaceae is strongly heterogeneous, and we suggest that the Costus radiation in the Neotropics arose at varied geographic contexts. PMID:27400627

  19. Possible method of aluminium speciation in forest soils.

    PubMed

    Drabek, Ondrej; Boruvka, Lubos; Mladkova, Lenka; Kocarek, Martin

    2003-09-15

    Labile Al forms and species can be a threat in acid soils due to their potential toxicity to plants. However, there is no universally accepted extraction method. Several extraction reagents for Al release from soil have been tested. KCl (0.5 or 1 M) is recommended for extraction of exchangeable Al, while 0.5 or 0.3 M CuCl(2) is suggested for extraction of 'weakly organically bound Al'. Both 0.1 and 0.05 M Na(4)P(2)O(7) are shown to be suitable for the extraction of 'total organically bound Al'. These extractions are relatively simple, robust, and applicable to different soils and soil horizons. In the second part of the paper, detailed speciation of exchangeable soil Al by means of an HPLC instrument equipped with an ion column (IC) is presented. An experimental set-up is described and tested on a set of samples. Interpretation of the speciation results is proposed, based on the separation of Al ions and Al complexes according to their charge. Speciation is shown to be dependent mainly on soil pH and organic matter quality. A general scheme of Al fractionation and speciation in soil is proposed. PMID:14507455

  20. LINKING WATERFOWL WITH CONTAMINANT SPECIATION IN RIPARIAN SOILS

    EPA Science Inventory

    This report summarizes the results of Mine Waste Technology Program (MWTP) Activity III, Project 38, Linking Waterfowl with Contaminant Speciation in Riparian Soils, implemented and funded by the U.S. Environmental Protection Agency (EPA) and jointly administered by EPA and the U...

  1. Speciation And Bioavailability Of Zinc In Amended Sediments

    EPA Science Inventory

    The speciation and bioavailability of zinc (Zn) in smelter-contaminated sediments was investigated as a function of phosphate (apatite) and organic amendment loading rate. Zinc species identified in preamendment sediment were zinc hydroxide-like phases, sphalerite, and zinc sorbe...

  2. Lead Speciation And Bioavailability In Apatite-Amended Sediments

    EPA Science Inventory

    The in situ sequestration of lead (Pb) in sediment with a phosphate amendment was investigated by Pb speciation and bioavailability. Sediment Pb in preamendment samples was identified as galena (PbS) with trace amounts of absorbed Pb. Sediment exposed to atmospheric conditions ...

  3. Transformation of heavy metal speciation during sludge drying: mechanistic insights

    SciTech Connect

    Weng, Huanxin; Ma, Xue-Wen; Fu, Feng-Xia; Zhang, Jin-Jun; Liu, Zan; Tian, Li-Xun; Liu, Chongxuan

    2014-01-30

    Speciation can fundamentally affect on the stability and toxicity of heavy metals in sludge from wastewater treatment plants. This research investigated the speciation of heavy metals in sludge from both municipal and industrial sources, and metal speciation change as a result of drying process to reduce sludge volume. The changes in sludge properties including sludge moisture content, temperature, density, and electrical conductivity were also monitored to provide insights into the mechanisms causing the change in heavy metal speciation. The results show that the drying process generally stabilized the Cr, Cu, Cd and Pb in sludge by transforming acid-soluble, reducible and oxidizable species into structurally stable forms. Such transformation and stabilization occurred regardless of the sludge source and type, and were primarily caused by the changes in sludge properties associated with decomposition of organic matter and sulfide. The results enhanced our understanding of the geochemical behavior of heavy metals in municipal sludge, and are useful for designing a treatment system for environment-friendly disposal of sludge.

  4. PM 2.5 ORGANIC SPECIATION INTERCOMPARISON RESULTS

    EPA Science Inventory

    This abstract describes a poster on results to a laboratory intercomparison of organic aerosol speciation analysis to be presented at the 2006 International Aerosol Conference sponsored by the American Association for Aerosol Research in St. Paul, Minnesota on September 10-15. T...

  5. Model inadequacy and mistaken inferences of trait-dependent speciation.

    PubMed

    Rabosky, Daniel L; Goldberg, Emma E

    2015-03-01

    Species richness varies widely across the tree of life, and there is great interest in identifying ecological, geographic, and other factors that affect rates of species proliferation. Recent methods for explicitly modeling the relationships among character states, speciation rates, and extinction rates on phylogenetic trees- BiSSE, QuaSSE, GeoSSE, and related models-have been widely used to test hypotheses about character state-dependent diversification rates. Here, we document the disconcerting ease with which neutral traits are inferred to have statistically significant associations with speciation rate. We first demonstrate this unfortunate effect for a known model assumption violation: shifts in speciation rate associated with a character not included in the model. We further show that for many empirical phylogenies, characters simulated in the absence of state-dependent diversification exhibit an even higher Type I error rate, indicating that the method is susceptible to additional, unknown model inadequacies. For traits that evolve slowly, the root cause appears to be a statistical framework that does not require replicated shifts in character state and diversification. However, spurious associations between character state and speciation rate arise even for traits that lack phylogenetic signal, suggesting that phylogenetic pseudoreplication alone cannot fully explain the problem. The surprising severity of this phenomenon suggests that many trait-diversification relationships reported in the literature may not be real. More generally, we highlight the need for diagnosing and understanding the consequences of model inadequacy in phylogenetic comparative methods. PMID:25601943

  6. Capillary electrophoresis application in metal speciation and complexation characterization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

  7. Speciation dynamics and biogeography of Neotropical spiral gingers (Costaceae).

    PubMed

    André, Thiago; Salzman, Shayla; Wendt, Tânia; Specht, Chelsea D

    2016-10-01

    Species can arise via the divisive effects of allopatry as well as due to ecological and/or reproductive character displacement within sympatric populations. Two separate lineages of Costaceae are native to the Neotropics; an early-diverging clade endemic to South America (consisting of ca. 16 species in the genera Monocostus, Dimerocostus and Chamaecostus); and the Neotropical Costus clade (ca. 50 species), a diverse assemblage of understory herbs comprising nearly half of total familial species richness. We use a robust dated molecular phylogeny containing most of currently known species to inform macroevolutionary reconstructions, enabling us to examine the context of speciation in Neotropical lineages. Analyses of speciation rate revealed a significant variation among clades, with a rate shift at the most recent common ancestor of the Neotropical Costus clade. There is an overall predominance of allopatric speciation in the South American clade, as most species display little range overlap. In contrast, sympatry is much higher within the Neotropical Costus clade, independent of node age. Our results show that speciation dynamics during the history of Costaceae is strongly heterogeneous, and we suggest that the Costus radiation in the Neotropics arose at varied geographic contexts.

  8. Speciation Mapping of Environmental Samples Using XANES Imaging

    EPA Science Inventory

    Fast X-ray detectors with large solid angles and high dynamic ranges open the door to XANES imaging, in which millions of spectra are collected to image the speciation of metals at micrometre resolution, over areas up to several square centimetres. This paper explores how such mu...

  9. The secondary contact phase of allopatric speciation in Darwin's finches

    PubMed Central

    Grant, Peter R.; Grant, B. Rosemary

    2009-01-01

    Speciation, the process by which two species form from one, involves the development of reproductive isolation of two divergent lineages. Here, we report the establishment and persistence of a reproductively isolated population of Darwin's finches on the small Galápagos Island of Daphne Major in the secondary contact phase of speciation. In 1981, an immigrant medium ground finch (Geospiza fortis) arrived on the island. It was unusually large, especially in beak width, sang an unusual song, and carried some Geospiza scandens alleles. We followed the fate of this individual and its descendants for seven generations over a period of 28 years. In the fourth generation, after a severe drought, the lineage was reduced to a single brother and sister, who bred with each other. From then on this lineage, inheriting unusual song, morphology, and a uniquely homozygous marker allele, was reproductively isolated, because their own descendants bred with each other and with no other member of the resident G. fortis population. These observations agree with some expectations of an ecological theory of speciation in that a barrier to interbreeding arises as a correlated effect of adaptive divergence in morphology. However, the important, culturally transmitted, song component of the barrier appears to have arisen by chance through an initial imperfect copying of local song by the immigrant. The study reveals additional stochastic elements of speciation, in which divergence is initiated in allopatry; immigration to a new area of a single male hybrid and initial breeding with a rare hybrid female. PMID:19918081

  10. Speciational view of macroevolution: Are micro and macroevolution decoupled?

    NASA Astrophysics Data System (ADS)

    Schwämmle, V.; Brigatti, E.

    2006-07-01

    We introduce a simple computational model that, with microscopic dynamics driven by natural selection and mutation alone, allows the description of true speciation events. A statistical analysis of the evolutionary tree so generated captures realistic features showing power laws for frequency distributions in time and size. Finally, some possible interpretations of the absence of punctuated dynamics with mass extinctions are worked out.

  11. A recombination suppressor contributes to ecological speciation in OSTRINIA moths.

    PubMed

    Wadsworth, C B; Li, X; Dopman, E B

    2015-06-01

    Despite unparalleled access to species' genomes in our post-genomic age, we often lack adequate biological explanations for a major hallmark of the speciation process-genetic divergence. In the presence of gene flow, chromosomal rearrangements such as inversions are thought to promote divergence and facilitate speciation by suppressing recombination. Using a combination of genetic crosses, phenotyping of a trait underlying ecological isolation, and population genetic analysis of wild populations, we set out to determine whether evidence supports a role for recombination suppressors during speciation between the Z and E strains of European corn borer moth (Ostrinia nubilalis). Our results are consistent with the presence of an inversion that has contributed to accumulation of ecologically adaptive alleles and genetic differentiation across roughly 20% of the Ostrinia sex chromosome (~4 Mb). Patterns in Ostrinia suggest that chromosomal divergence may involve two separate phases-one driving its transient origin through local adaptation and one determining its stable persistence through differential introgression. As the evolutionary rate of rearrangements in lepidopteran genomes appears to be one of the fastest among eukaryotes, structural mutations may have had a disproportionate role during adaptive divergence and speciation in Ostrinia and in other moths and butterflies. PMID:25626887

  12. The role of gene expression in ecological speciation

    PubMed Central

    Pavey, Scott A; Collin, Hélène; Nosil, Patrik; Rogers, Sean M

    2010-01-01

    Ecological speciation is the process by which barriers to gene flow between populations evolve due to adaptive divergence via natural selection. A relatively unexplored area in ecological speciation is the role of gene expression. Gene expression may be associated with ecologically important phenotypes not evident from morphology and play a role during colonization of new environments. Here we review two potential roles of gene expression in ecological speciation: (1) its indirect role in facilitating population persistence and (2) its direct role in contributing to genetically based reproductive isolation. We find indirect evidence that gene expression facilitates population persistence, but direct tests are lacking. We also find clear examples of gene expression having effects on phenotypic traits and adaptive genetic divergence, but links to the evolution of reproductive isolation itself remain indirect. Gene expression during adaptive divergence seems to often involve complex genetic architectures controlled by gene networks, regulatory regions, and “eQTL hotspots.” Nonetheless, we review how approaches for isolating the functional mutations contributing to adaptive divergence are proving to be successful. The study of gene expression has promise for increasing our understanding ecological speciation, particularly when integrative approaches are applied. PMID:20860685

  13. EXAMINATION OF CHANGES IN AS SPECIATION IN SULFIDIC SOLUTIONS

    EPA Science Inventory

    The fate of arsenic (As) in the environment, its bioavailability and toxicity is fundamentally linked to its speciation. As in aerobic environments is predominantly arsenate (As(V)), however under reducing conditions arsenite (As(III)) species dominate. In sulfidic environments t...

  14. Arsenic Concentrations and Speciation in Shellfishes from Korea

    NASA Astrophysics Data System (ADS)

    Yoon, C.; Yoon, H.

    2005-12-01

    Speciation of arsenic has received significant attention over the past 20 years in both mechanistic and exposure assessment research. Because the toxicity of arsenic is related to its oxidation state and its chemical forms, the determination of the total arsenic contents in a sample is not adequate to allow its impact on living organisms to be estimated. The inorganic arsenic species, arsenite (As3+) and arsenate (As5+), have been classified as carcinogenic and the methylated forms, monomethyl arsonic acid (MMA) and dimethyl arsinic acid (DMA) have recently been identified as cancer promoters. The highly methylated compounds like as arsenobetaine (AsB) and arsenocholine (AsC) are considered to be nontoxic. Although organisms in marine environment contain high amounts of total arsenic (ppm level), it is not usually present as inorganic arsenic or simple methylated forms well known as one of the toxic species. Arsenobetaine is the dominant species in marine animals and arsenosugars are most abundant in marine algae. This study aims to clarify those arsenic species present in the whole body of eleven different shellfishes from Korea. And those arsenic species were separated and measured by characterization using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) coupled system. The separation of arsenic species was achieved on anion exchange column and cation exchange column using phosphate and pyridine eluent, respectively. The ultrasonic extraction was employed for extraction of arsenic from whole body of shellfishes. The method was validated by analyzing three certified reference materials (DORM-2, TORT-2, 1566b). Total arsenic concentrations ranged from 0.1 mg/kg dry mass to 21.7 mg/kg dry mass. Most marine shellfishes contained higher arsenobetaine and arsenocholine with the exception of two shellfishes living in river. The lower amounts of inorganic arsenic species were also found in the some sample extracts

  15. Hydrocarbon emissions speciation in diesel and biodiesel exhausts

    NASA Astrophysics Data System (ADS)

    Payri, Francisco; Bermúdez, Vicente R.; Tormos, Bernardo; Linares, Waldemar G.

    Diesel engine emissions are composed of a long list of organic compounds, ranging from C 2 to C 12+, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic. The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed. Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed. The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum

  16. Evaluation of a combined fractionation and speciation approach for study of size-based distribution of organotin species on environmental colloids.

    PubMed

    Dubascoux, Stéphane; Heroult, Julien; Le Hécho, Isabelle; Potin-Gautier, Martine; Lespes, Gaëtane

    2008-04-01

    Results relating to the first original application of an analytical approach combining asymmetric flow field-flow fractionation (As-Fl-FFF) with multi-detection and chemical speciation for determination of organotins in a landfill leachate sample are presented. The speciation analysis involved off-line head-space solid-phase microextraction (HS-SPME)-gas chromatography with pulsed-flame photometric detection (GC-PFPD) performed after three consecutive collections of five different fractions of interest from the As-Fl-FFF system and cross-flow part (assumed to be representative of the <10 kDa phase). After 0.45 microm filtration and without preconcentration before fractionation and speciation analysis, limits of detection (LOD) were 4-45 ng (Sn) L(-1) in the sample, with relative standard deviations (RSD) of 3-23%. The As-Fl-FFF fractionation of this sample enables characterization of two distinct populations-organic-rich and inorganic colloids with gyration radius up to 120 nm. Total Sn and mono and dibutyltins (MBT and DBT) appear to be distributed over the whole colloidal phase. Tributyl, monomethyl, monooctyl, and diphenyltins (TBT, MMT, MOcT, and DPhT) were also detected. Quantitative speciation analysis performed on the two colloidal populations and in the <10 kDa phase revealed concentrations from 130 +/- 10 (MMT) to 560 +/- 50 ng (Sn) L(-1) (DPhT). PMID:18273605

  17. Temporal variation of iodine concentration and speciation (127I and 129I) in wetland groundwater from the Savannah River Site, USA.

    PubMed

    Zhang, Saijin; Ho, Yi-Fang; Creeley, Danielle; Roberts, Kimberly A; Xu, Chen; Li, Hsiu-Ping; Schwehr, Kathleen A; Kaplan, Daniel I; Yeager, Chris M; Santschi, Peter H

    2014-10-01

    (129)I derived from a former radionuclide disposal basin located on the Savannah River Site (SRS) has concentrated in a wetland 600 m downstream. To evaluate temporal environmental influences on iodine speciation and mobility in this subtropical wetland environment, groundwater was collected over a three-year period (2010-2012) from a single location. Total (127)I and (129)I showed significant temporal variations, ranging from 68-196 nM for (127)I and <5-133 pCi/L for (129)I. These iodine isotopes were significantly correlated with groundwater acidity and nitrate, two parameters elevated within the contaminant plume. Additionally, (129)I levels were significantly correlated with those of (127)I, suggesting that biogeochemical controls on (127)I and (129)I are similar within the SRS aquifer/wetland system. Iodine speciation demonstrates temporal variations as well, reflecting effects from surface recharges followed by acidification of groundwater and subsequent formation of anaerobic conditions. Our results reveal a complex system where few single ancillary parameters changed in a systematic manner with iodine speciation. Instead, changes in groundwater chemistry and microbial activity, driven by surface hydrological events, interact to control iodine speciation and mobility. Future radiological risk models should consider the flux of (129)I in response to temporal changes in wetland hydrologic and chemical conditions.

  18. Evaluation of a combined fractionation and speciation approach for study of size-based distribution of organotin species on environmental colloids.

    PubMed

    Dubascoux, Stéphane; Heroult, Julien; Le Hécho, Isabelle; Potin-Gautier, Martine; Lespes, Gaëtane

    2008-04-01

    Results relating to the first original application of an analytical approach combining asymmetric flow field-flow fractionation (As-Fl-FFF) with multi-detection and chemical speciation for determination of organotins in a landfill leachate sample are presented. The speciation analysis involved off-line head-space solid-phase microextraction (HS-SPME)-gas chromatography with pulsed-flame photometric detection (GC-PFPD) performed after three consecutive collections of five different fractions of interest from the As-Fl-FFF system and cross-flow part (assumed to be representative of the <10 kDa phase). After 0.45 microm filtration and without preconcentration before fractionation and speciation analysis, limits of detection (LOD) were 4-45 ng (Sn) L(-1) in the sample, with relative standard deviations (RSD) of 3-23%. The As-Fl-FFF fractionation of this sample enables characterization of two distinct populations-organic-rich and inorganic colloids with gyration radius up to 120 nm. Total Sn and mono and dibutyltins (MBT and DBT) appear to be distributed over the whole colloidal phase. Tributyl, monomethyl, monooctyl, and diphenyltins (TBT, MMT, MOcT, and DPhT) were also detected. Quantitative speciation analysis performed on the two colloidal populations and in the <10 kDa phase revealed concentrations from 130 +/- 10 (MMT) to 560 +/- 50 ng (Sn) L(-1) (DPhT).

  19. DEVELOPMENT OF FINE PARTICULATE EMISSION FACTORS AND SPECIATION PROFILES FOR OIL AND GAS FIRED COMBUSTION SYSTEMS

    SciTech Connect

    Glenn England; Oliver Chang; Stephanie Wien

    2002-02-14

    This report provides results from the second year of this three-year project to develop dilution measurement technology for characterizing PM2.5 (particles with aerodynamic diameter smaller than 2.5 micrometers) and precursor emissions from stationary combustion sources used in oil, gas and power generation operation. Detailed emission rate and chemical speciation tests results for a gas turbine, a process heater, and a commercial oil/gas fired boiler are presented. Tests were performed using a research dilution sampling apparatus and traditional EPA methods. A series of pilot tests were conducted to identify the constraints to reduce the size of current research dilution sampler for future stack emission tests. Based on the test results, a bench prototype compact dilution sampler developed and characterized in GE EER in August 2002.

  20. Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution.

    PubMed

    Bera, Mrinal K; Antonio, Mark R

    2015-05-19

    Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu(3+) cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achieved by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.

  1. Utility of EXAFS in characterization and speciation of mercury-bearing mine wastes

    USGS Publications Warehouse

    Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

    1999-01-01

    Extensive mining of large mercury deposits located in the California Coast Range has resulted in mercury contamination of both the local environment and water supplies. The solubility, dispersal, and ultimate fate of mercury are all affected by its chemical speciation, which can be most readily determined in a direct fashion using EXAFS spectroscopy. EXAFS spectra of mine wastes collected from several mercury mines in the California Coast Range with mercury concentrations ranging from 230 to 1060 mg/kg (ppm) have been analyzed using a spectral database of mercury minerals and sorbed mercury complexes. While some calcines have been found to consist almost exclusively of mercuric sulfide, HgS, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. This experimental approach can provide a quantitative measurement of the mercury compounds present and may serve as an indicator of the bioavailability and toxicity levels of mercury mine wastes.

  2. The effect of pH on phosphorus availability and speciation in an aquaponics nutrient solution.

    PubMed

    Cerozi, Brunno da Silva; Fitzsimmons, Kevin

    2016-11-01

    The interaction between the main ions in aquaponics nutrient solutions affects chemical composition and availability of nutrients, and nutrient uptake by plant roots. This study determined the effect of pH on phosphorus (P) speciation and availability in an aquaponics nutrient solution and used Visual MINTEQ to simulate P species and P activity. In both experimental and simulated results, P availability decreased with increase in pH of aquaponics nutrient solutions. According to simulations, P binds to several cations leaving less free phosphate ions available in solution. High pH values resulted in the formation of insoluble calcium phosphate species. The study also demonstrated the importance of organic matter and alkalinity in keeping free phosphate ions in solution at high pH ranges. It is recommended though that pH in aquaponics systems is maintained at a 5.5-7.2 range for optimal availability and uptake by plants.

  3. The effect of pH on phosphorus availability and speciation in an aquaponics nutrient solution.

    PubMed

    Cerozi, Brunno da Silva; Fitzsimmons, Kevin

    2016-11-01

    The interaction between the main ions in aquaponics nutrient solutions affects chemical composition and availability of nutrients, and nutrient uptake by plant roots. This study determined the effect of pH on phosphorus (P) speciation and availability in an aquaponics nutrient solution and used Visual MINTEQ to simulate P species and P activity. In both experimental and simulated results, P availability decreased with increase in pH of aquaponics nutrient solutions. According to simulations, P binds to several cations leaving less free phosphate ions available in solution. High pH values resulted in the formation of insoluble calcium phosphate species. The study also demonstrated the importance of organic matter and alkalinity in keeping free phosphate ions in solution at high pH ranges. It is recommended though that pH in aquaponics systems is maintained at a 5.5-7.2 range for optimal availability and uptake by plants. PMID:27575336

  4. Speciation of non-methane hydrocarbons (NMHCs) from anthropogenic sources in Beirut, Lebanon.

    PubMed

    Salameh, T; Afif, C; Sauvage, S; Borbon, A; Locoge, N

    2014-09-01

    The chemical composition of emissions from the different anthropogenic sources of non-methane hydrocarbons (NMHC) is essential for modeling and source apportionment studies. The speciated profiles of major NMHC sources in Lebanon, including road transport, gasoline vapor, power generation, and solvent use were established. Field sampling have been carried out by canisters in 2012. Around 67 NMHC (C2 to C9) were identified and quantified by using a gas chromatograph equipped with a flame ionization detector. Typical features of the roadway emissions included high percentages of isopentane, butane, toluene, xylenes, ethylene, and ethyne. Gasoline evaporation profiles included high percentage of the C4-C5 saturated hydrocarbons reaching 59 %. The main compounds of the power generator emissions are related to combustion. Toluene and C8-C9 aromatics were the most abundant species in emissions from paint applications. Finally, the impact of the use of region-specific source profile is tackled regarding the implication on air quality. PMID:24833189

  5. Speciation of technetium(IV) in bicarbonate media.

    PubMed

    Alliot, Isabelle; Alliot, Cyrille; Vitorge, Pierre; Fattahi, Massoud

    2009-12-15

    The technetium isotope (99)Tc is a major fission product from nuclear reactors. Ultimately it is disposed of as radioactive waste since it has few applications outside of scientific research. Geochemical modeling of the dissolution of nuclear waste and of the solubility and speciation of the dissolved radionuclides in groundwater is an important part of the Performance Assessment for the safety of nuclear waste repositories. It relies on the availability of a critically assessed thermodynamic database. The potential of the Tc(VII)/Tc(IV) redox couple is measured here under various chemical conditions to verify the stoichiometries of Tc complexes and determine their stabilities: (i) -log(10)[H(+)] in the range 7.0-10.0, for 0.3, 0.6, and 0.7 M [CO(3)](total); (ii) [CO(3)](total) in the range 0.01-0.6 M at -log(10)[H(+)] approximately 8.6; and (iii) [Tc(VII)]/[Tc(IV] ratios of (6.02 10(-5) M)/(10(-6) M) and (6.02 10(-5) M)/(6.02 10(-5) M) at -log(10)[H(+)] = -9.1 and [CO(3)](total) = 1 M. Assuming that Tc(VII), TcO(4)(-) is the only species which exists under all the above chemical conditions, the potentiometric results can be interpreted by considering the presence of two hydroxide-carbonate monomeric complexes. The hydrolysis equilibrium between these two complexes is Tc(CO(3))(OH)(2) + H(2)O <--> Tc(CO(3))(OH)(3)(-) + H(+) with -log(10)[H(+)](1/2) = 8.69 +/- 0.20, which is consistent with the -8.3 +/- 0.6 corresponding hydrolysis constant of the NEA TDB review. 733 +/- 44 mV/SHE and 575 +/- 60 mV/SHE are measured for the standard potentials of the TcO(4)(-)/Tc(CO(3))(OH)(2), and for the TcO(4)(-)/Tc(CO(3))(OH)(3)(-) redox couples respectively. The corresponding formation constants from TcO(OH)(2) are log(10)K(1,2) = 19.8 +/- 0.5 and log(10)K(1,3) = 10.5 +/- 0.5, to be compared with the 19.3 +/- 0.3 and 11.0 +/- 0.6 values proposed by the NEA TDB review. Note that these values have been converted for the formation reactions described here, thus the given values are

  6. A new method for the characterisation and quantitative speciation of base metal smelter stack particulates.

    PubMed

    Skeaff, James M; Thibault, Yves; Hardy, David J

    2011-06-01

    Base metal smelters may be a source of particulates containing metals of environmental concern released to the atmosphere. Knowledge of the quantitative chemical speciation of particulate releases from base metal smelters will be of value in smelter emission fingerprinting, site-specific risk assessments, predictions of the behaviour of smelter stack particulates released to the environment and in resolving liability issues related to current and historic releases. Accordingly, we have developed an innovative approach comprising bulk chemical analysis, a leaching procedure, X-ray diffraction analysis and scanning electron microscopy/electron probe microanalysis characterisation in a step-wise apportioning procedure to derive the quantitative speciation of particulate samples from the stacks of three copper smelters designated as A, B and C. For the A smelter stack particulates, the major calculated percentages were 29 CuSO(4), 20 ZnSO(4).H(2)O, 13 (Cu(0.94)Zn(0.06))(2)(AsO(4))(OH), 11 PbSO(4) and four As(2)O(3). For the B smelter stack particulates, the primary calculated percentages were 20 ZnSO(4).H(2)O, 20 PbSO(4), 12 CuSO(4) and nine As(2)O(3). Finally, we calculated that the C smelter stack particulates mostly comprised 34 ZnSO(4).H(2)O, 19 (Cu(0.84)Zn(0.16))(AsO(3)OH), 11 PbSO(4), 10 As(2)O(3) and nine Zn(3)(AsO(4))(2). Between 56% and 67% by weight of the smelter stack particulates, including the As, was soluble in water. For these and other operations, the data and approach may be useful in estimating metals partitioning among water, soil and sediment, as well as predictions of the effects of the stack particulates released to the environment. PMID:20676929

  7. Comparison of Al speciation and other soil characteristics between meadow, young forest and old forest stands.

    PubMed

    Dlouhá, Sárka; Borůvka, Lubos; Pavlů, Lenka; Tejnecký, Václav; Drábek, Ondrej

    2009-11-01

    The aim of this paper is to describe the influence of spruce (Picea abies) afforestation on soil chemical properties, especially on soil acidity and aluminium (Al) mobilization and speciation in soil. For our study we used a unique set of three adjacent plots, including a meadow and two spruce forest stands of different age, in otherwise comparable conditions. The plots were located in the region of Giant Mountains, north-eastern Czech Republic. In general, pH values decreased and Al concentrations increased significantly after afforestation. Speciation of KCl-extractable and water-soluble Al in soil samples was done by means of HPLC/IC method. The concentrations of Al(X)(1+) and Al(Y)(2+) forms (in both extracts) are higher in humic and organically enriched (Bhs) horizons. The highest concentration of Al(3+) in both extracts is in the B horizons of old forest. Generally, in all studied stands majority of Al in aqueous extract is in the Al(X)(1+) form, which indicates that a large amount of mobile Al is bound in organic complexes. It suggests that actual toxicity is rather low. On the other hand, we have proved that majority of KCl-extractable Al exists in Al(3+) form. Thus we can conclude that disturbance of existing equilibrium may cause massive release of highly toxic Al(3+) from soil sorption complex to the soil solution, and consequently it can endanger the whole ecosystem. Moreover, continuous soil acidification accelerated by anthropogenic factors leading to Al mobilization represents a chemical time bomb. PMID:19748129

  8. Lead toxicity to Lemna minor predicted using a metal speciation chemistry approach.

    PubMed

    Antunes, Paula M C; Kreager, Nancy J

    2014-10-01

    In the present study, predictive measures for Pb toxicity and Lemna minor were developed from bioassays with 7 surface waters having varied chemistries (0.5-12.5 mg/L dissolved organic carbon, pH of 5.4-8.3, and water hardness of 8-266 mg/L CaCO3 ). As expected based on water quality, 10%, 20%, and 50% inhibitory concentration (IC10, IC20, and IC50, respectively) values expressed as percent net root elongation (%NRE) varied widely (e.g., IC20s ranging from 306 nM to >6920 nM total dissolved Pb), with unbounded values limited by Pb solubility. In considering chemical speciation, %NRE variability was better explained when both Pb hydroxides and the free lead ion were defined as bioavailable (i.e., f{OH} ) and colloidal Fe(III)(OH)3 precipitates were permitted to form and sorb metals (using FeOx as the binding phase). Although cause and effect could not be established because of covariance with alkalinity (p = 0.08), water hardness correlated strongly (r(2)  = 0.998, p < 0.0001) with the concentration of total Pb in true solution ([Pb]T_True solution ). Using these correlations as the basis for predictions (i.e., [Pb]T_True solution vs water hardness and %NRE vs f{OH} ), IC20 and IC50 values produced were within a factor of 2.9 times and 2.2 times those measured, respectively. The results provide much needed effect data for L. minor and highlight the importance of chemical speciation in Pb-based risk assessments for aquatic macrophytes.

  9. First-principles study of boron speciation in calcite and aragonite

    NASA Astrophysics Data System (ADS)

    Balan, Etienne; Pietrucci, Fabio; Gervais, Christel; Blanchard, Marc; Schott, Jacques; Gaillardet, Jérome

    2016-11-01

    Despite the importance of boron as a proxy of past ocean pH, the crystal-chemical factors controlling its incorporation in the structure of calcium carbonates are still poorly understood. This is partly linked to an imperfect knowledge of the coordination, protonation state and local environment of boron species in these minerals. In the present study, we use first-principles quantum mechanical tools to model selected trigonal and tetragonal boron species in calcite and aragonite. The stable geometry of the models is obtained from standard energy minimization schemes or using a more advanced metadynamics exploration of their configurational space. The computation of 11B NMR chemical shifts and quadrupolar coupling parameters enables a straightforward comparison of the models to existing experimental NMR data. The results show that B in calcium carbonates does occur as structural species substituted for CO32- anions. The B speciation depends on the polymorph considered. In calcite, structural boron is present as partially deprotonated trigonal BO2(OH)2- species coexisting with a fraction of substituted B(OH)4- groups. In aragonite, the B(OH)4- substitution for CO32- anions is dominant. Different species, including entrapped B(OH)3 molecules and substituted BO33- groups also occur in biogenic samples. The diversity of B speciation reflects a diversity of B incorporation mechanisms and sheds light on previous studies confronting B isotopic composition determination with NMR observations. The mechanisms of boron incorporation in calcium carbonates are probably more complex than usually assumed in the literature using boron isotopes as a proxy of paleo-atmospheric CO2 reconstructions. Although not invalidating the empirical paleo-pH proxy, these results call for a better understanding of the fundamental mechanisms of boron incorporation in carbonates.

  10. Lead toxicity to Lemna minor predicted using a metal speciation chemistry approach.

    PubMed

    Antunes, Paula M C; Kreager, Nancy J

    2014-10-01

    In the present study, predictive measures for Pb toxicity and Lemna minor were developed from bioassays with 7 surface waters having varied chemistries (0.5-12.5 mg/L dissolved organic carbon, pH of 5.4-8.3, and water hardness of 8-266 mg/L CaCO3 ). As expected based on water quality, 10%, 20%, and 50% inhibitory concentration (IC10, IC20, and IC50, respectively) values expressed as percent net root elongation (%NRE) varied widely (e.g., IC20s ranging from 306 nM to >6920 nM total dissolved Pb), with unbounded values limited by Pb solubility. In considering chemical speciation, %NRE variability was better explained when both Pb hydroxides and the free lead ion were defined as bioavailable (i.e., f{OH} ) and colloidal Fe(III)(OH)3 precipitates were permitted to form and sorb metals (using FeOx as the binding phase). Although cause and effect could not be established because of covariance with alkalinity (p = 0.08), water hardness correlated strongly (r(2)  = 0.998, p < 0.0001) with the concentration of total Pb in true solution ([Pb]T_True solution ). Using these correlations as the basis for predictions (i.e., [Pb]T_True solution vs water hardness and %NRE vs f{OH} ), IC20 and IC50 values produced were within a factor of 2.9 times and 2.2 times those measured, respectively. The results provide much needed effect data for L. minor and highlight the importance of chemical speciation in Pb-based risk assessments for aquatic macrophytes. PMID:25044009

  11. Speciation of antimony in polyethylene terephthalate bottles

    SciTech Connect

    Martin, R.R.; Ablett, J.; Shotyk, W.S.; Naftel, S.; Northrup, P.

    2009-12-18

    Antimony contamination has been reported in drinking water from polyethylene terephthalate (PET) bottles. Micro-X-ray fluorescence (XRF) analysis has been used to identify the distribution and chemical form of residual antimony used as a catalyst in the manufacture of PET bottles. The results are consistent with clusters of Sb(III) having dimensions of the order of tens of micrometers, clearly showing the ability of synchrotron radiation analyses to both map elemental distribution and determine oxidation state.

  12. Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

    PubMed

    Batuk, Olga N; Conradson, Steven D; Aleksandrova, Olga N; Boukhalfa, Hakim; Burakov, Boris E; Clark, David L; Czerwinski, Ken R; Felmy, Andrew R; Lezama-Pacheco, Juan S; Kalmykov, Stepan N; Moore, Dean A; Myasoedov, Boris F; Reed, Donald T; Reilly, Dallas D; Roback, Robert C; Vlasova, Irina E; Webb, Samuel M; Wilkerson, Marianne P

    2015-06-01

    The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment. PMID:25815708

  13. Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

    PubMed

    Batuk, Olga N; Conradson, Steven D; Aleksandrova, Olga N; Boukhalfa, Hakim; Burakov, Boris E; Clark, David L; Czerwinski, Ken R; Felmy, Andrew R; Lezama-Pacheco, Juan S; Kalmykov, Stepan N; Moore, Dean A; Myasoedov, Boris F; Reed, Donald T; Reilly, Dallas D; Roback, Robert C; Vlasova, Irina E; Webb, Samuel M; Wilkerson, Marianne P

    2015-06-01

    The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

  14. SUBSURFACE MOBILE PLUTONIUM SPECIATION: SAMPLING ARTIFACTS FOR GROUNDWATER COLLOIDS

    SciTech Connect

    Kaplan, D.; Buesseler, K.

    2010-06-29

    A recent review found several conflicting conclusions regarding colloid-facilitated transport of radionuclides in groundwater and noted that colloids can both facilitate and retard transport. Given these contrasting conclusions and the profound implications even trace concentrations of plutonium (Pu) have on the calculated risk posed to human health, it is important that the methodology used to sample groundwater colloids be free of artifacts. The objective of this study was: (1) to conduct a field study and measure Pu speciation, ({sup 239}Pu and {sup 240}Pu for reduced-Pu{sub aq}, oxidized-Pu{sub aq}, reduced-Pu{sub colloid}, and oxidized-Pu{sub colloid}), in a Savannah River Site (SRS) aquifer along a pH gradient in F-Area, (2) to determine the impact of pumping rate on Pu concentration, Pu speciation, and Pu isotopic ratios, (3) determine the impact of delayed sample processing (as opposed to processing directly from the well).

  15. Speciation of uranium(VI) sorption complexes on montmorillonite

    SciTech Connect

    Chisholm-Brause, C.J.; Morris, D.E.; Richard, R.E.

    1992-05-01

    Environmental contaminant releases that contain uranium are among the most serious problems that must be confronted by restoration programs. To facilitate restoration, information concerning the speciation of uranium is needed. Under oxidizing conditions, dissolved uranium is predominantly in the U(VI) (uranyl) form and is quite mobile in the environment, however sorption onto soils may retard its movement. In this study, we have investigated the effects of changes in solution speciation on the nature of uranyl sorption complexes on montmorillonite, a common soil constituent. Aqueous U(VI) solutions between pH 3 to 7 were batch-equilibrated with montmorillonite for several days; specific pH values were selected such that the solutions consisted of dominantly monomeric, oligomeric, or a mix of monomeric and oligomeric aqueous uranyl species. Emission spectroscopy was used to investigate the nature of U(VI) sorbed to montmorillonite.

  16. Speciation of uranium in compartments of living cells.

    PubMed

    Geipel, Gerhard; Viehweger, Katrin

    2015-06-01

    Depleted uranium used as ammunition corrodes in the environment forming mineral phases and then dissolved uranium species like uranium carbonates (Schimmack et al., in Radiat Environ Biophys 46:221-227, 2007) and hydroxides. These hydroxide species were contacted with plant cells (canola). After 24 h contact time the cells were fractionated and the uranium speciation in the fraction was determined by time resolved laser-induced fluorescence spectroscopy at room temperature as well at 150 K. It could be shown that the uranium speciation in the fractions is different to that in the nutrient solution. Comparison of the emission bands with literature data allows assignment of the uranium binding forms.

  17. Polymorphic butterfly reveals the missing link in ecological speciation

    PubMed Central

    Chamberlain, Nicola L.; Hill, Ryan I.; Kapan, Durrell D.; Gilbert, Lawrence E.; Kronforst, Marcus R.

    2010-01-01

    Ecological speciation occurs when ecologically-based divergent selection causes the evolution of reproductive isolation. While there are many empirical examples of this process, there exists a poorly characterized stage during which the traits that distinguish species ecologically and reproductively segregate in a single population. Using a combination of genetic mapping, mate choice experiments, field observations, and population genetics, we studied a butterfly population with a mimetic wing color polymorphism and found that they exhibited partial color-based assortative mate preference. These traits represent the divergent, ecologically-based signal and preference components of sexual isolation that usually distinguish incipient and sibling species. The association between behavior and recognition trait in a single population may enhance the probability of speciation and provides an example for the missing link between an interbreeding population and isolated species. PMID:19892982

  18. Sexual selection accelerates signal evolution during speciation in birds

    PubMed Central

    Seddon, Nathalie; Botero, Carlos A.; Tobias, Joseph A.; Dunn, Peter O.; MacGregor, Hannah E. A.; Rubenstein, Dustin R.; Uy, J. Albert C.; Weir, Jason T.; Whittingham, Linda A.; Safran, Rebecca J.

    2013-01-01

    Sexual selection is proposed to be an important driver of diversification in animal systems, yet previous tests of this hypothesis have produced mixed results and the mechanisms involved remain unclear. Here, we use a novel phylogenetic approach to assess the influence of sexual selection on patterns of evolutionary change during 84 recent speciation events across 23 passerine bird families. We show that elevated levels of sexual selection are associated with more rapid phenotypic divergence between related lineages, and that this effect is restricted to male plumage traits proposed to function in mate choice and species recognition. Conversely, we found no evidence that sexual selection promoted divergence in female plumage traits, or in male traits related to foraging and locomotion. These results provide strong evidence that female choice and male–male competition are dominant mechanisms driving divergence during speciation in birds, potentially linking sexual selection to the accelerated evolution of pre-mating reproductive isolation. PMID:23864596

  19. Sexual selection accelerates signal evolution during speciation in birds.

    PubMed

    Seddon, Nathalie; Botero, Carlos A; Tobias, Joseph A; Dunn, Peter O; Macgregor, Hannah E A; Rubenstein, Dustin R; Uy, J Albert C; Weir, Jason T; Whittingham, Linda A; Safran, Rebecca J

    2013-09-01

    Sexual selection is proposed to be an important driver of diversification in animal systems, yet previous tests of this hypothesis have produced mixed results and the mechanisms involved remain unclear. Here, we use a novel phylogenetic approach to assess the influence of sexual selection on patterns of evolutionary change during 84 recent speciation events across 23 passerine bird families. We show that elevated levels of sexual selection are associated with more rapid phenotypic divergence between related lineages, and that this effect is restricted to male plumage traits proposed to function in mate choice and species recognition. Conversely, we found no evidence that sexual selection promoted divergence in female plumage traits, or in male traits related to foraging and locomotion. These results provide strong evidence that female choice and male-male competition are dominant mechanisms driving divergence during speciation in birds, potentially linking sexual selection to the accelerated evolution of pre-mating reproductive isolation.

  20. Quantifying variation in speciation and extinction rates with clade data.

    PubMed

    Paradis, Emmanuel; Tedesco, Pablo A; Hugueny, Bernard

    2013-12-01

    High-level phylogenies are very common in evolutionary analyses, although they are often treated as incomplete data. Here, we provide statistical tools to analyze what we name "clade data," which are the ages of clades together with their numbers of species. We develop a general approach for the statistical modeling of variation in speciation and extinction rates, including temporal variation, unknown variation, and linear and nonlinear modeling. We show how this approach can be generalized to a wide range of situations, including testing the effects of life-history trait