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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. Chemical Speciation of Chromium in Drilling Muds

    SciTech Connect

    Taguchi, Takeyoshi; Yoshii, Mitsuru; Shinoda, Kohzo

    2007-02-02

    Drilling muds are made of bentonite and other clays, and/or polymers, mixed with water to the desired viscosity. Without the drilling muds, corporations could not drill for oil and gas and we would have hardly any of the fuels and lubricants considered essential for modern industrial civilization. There are hundreds of drilling muds used and some kinds of drilling muds contain chromium. The chemical states of chromium in muds have been studied carefully due to concerns about the environmental influence. However it is difficult to determine the chemical state of chromium in drilling muds directly by conventional analytical methods. We have studied the chemical form of chromium in drilling muds by using a laboratory XAFS system and a synchrotron facility.

  3. GEOCHEM-EZ: a chemical speciation program with greater power and flexibility

    Technology Transfer Automated Retrieval System (TEKTRAN)

    GEOCHEM –EZ is a multi-functional chemical speciation program, which was designed to replace the existing GEOCHEM-PC, a program that can only be used on DOS consoles. Chemical speciation programs, such as GEOCHEM (Sposito and Mattigod, 1980) and GEOCHEM-PC (Parker et al., 1995), have been excellent ...

  4. 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...

  5. Survey of chemical speciation of trace elements using synchrotron radiation

    SciTech Connect

    Gordon, B.M.

    1985-01-01

    Information concerning the chemical state of trace elements in biological systems generally has not been available. Such information for toxic elements and metals in metalloproteins could prove extremely valuable in the elucidation of their metabolism and other biological processes. The shielding of core electrons by binding electrons affect the energy required for creating inner-shell holes. Furthermore, the molecular binding and the symmetry of the local environment of an atom affect the absorption spectrum in the neighborhood of the absorption edge. X-ray absorption near-edge structure (XANES) using synchrotron radiation excitation can be used to provide chemical speciation information for trace elements at concentrations as low as 10 ppM. The structure and position of the absorption curve in the region of an edge can yield vital data about the local structure and oxidation state of the trace element in question. Data are most easily interpreted by comparing the observed edge structure and position with those of model compounds of the element covering the entire range of possible oxidation states. Examples of such analyses are reviewed. 14 refs., 1 fig.

  6. 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.

  7. 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., Jr.

    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.

  8. 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

  9. 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...

  10. 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...

  11. Plasma mass spectrometry as a detector for chemical speciation studies.

    PubMed

    Tomlinson, M J; Lin, L; Caruso, J A

    1995-03-01

    Inductively coupled plasma mass spectrometry (ICP-MS), when coupled with the unique separating power of various chromatographic techniques, allows the detection of various elements at ultra-trace levels. The investigation of various toxic elements of environmental concern coupling relatively recent techniques, such as supercritical fluid chromatography (SFC) and capillary zone electrophoresis (CZE), to ICP-MS, is discussed. Comparisons have been made with detection limits obtained by using the flame ionization detector. The conventional technique of liquid chromatography for the speciation of vanadium, chromium and nickel is also discussed. PMID:7741220

  12. Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses.

    PubMed

    Kumpiene, Jurate; Robinson, Ryan; Brännvall, Evelina; Nordmark, Désirée; Bjurström, Henrik; Andreas, Lale; Lagerkvist, Anders; Ecke, Holger

    2011-01-01

    Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment. PMID:20630737

  13. CHEMICAL SPECIATION OF FLUE GAS DESULFURIZATION SLUDGE CONSTITUENTS

    EPA Science Inventory

    This project addresses the problem of flue gas desulfurization (FGD) sludge disposal to land. Specifically, the chemical species of FGD sludge constituents are thermodynamically modeled using the equilibrium constant approach, in an attempt to predict the constituent concentratio...

  14. [Determination the chemical speciation of Cu, Zn, Fe and Mn in Radix Scutellariae by AAS].

    PubMed

    Miao, Shan; Sun, Ji-yuan; Xie, Yan-hua; Wang, Jian-bo; Shi, Xiao-peng; Ding, Yuan-yuan; Bi, Lin-lin; Gao, Shuang-bin; Wang, Si-wang

    2009-05-01

    An analysis method was developed to determine the chemical speciation of Cu, Zn, Fe and Mn in radix scutellariae decoction using atomic absorption spectroscopy(AAS). The decoction can be divided into suspension and soluble species by 0.45 microm filter membrane and the soluble species can be separated into organism and inorganic species by LSA-10 macroporous resin. These elements in water-soluble test samples can be divided into alcohol-soluble and water-soluble by adopting n-octyl alcohol-water allocation system in man-made gastric acidity. Then, the concentration of these elements was determined by AAS, which provided more chemical speciation information about these elements instead of the total amount of them only in radix scutellariae. Deteotion limit of Cu, Zn and Mn by using the method was all 0.01 microg x mL(-1) and was 0.02 microg x mL(-1) for Fe. The RSD was in the range of 1.5%-3.6% (n=11) and the recovery rate of soluble species and inorganic species were in range of 96.7%-105.0%. The method has been successfully applied to determine the chemical speciation of Cu, Zn, Fe and Mn in radix scutellariae, which was very important for overall study of radix scutellariae. PMID:19650506

  15. CHEMICAL SPECIATION OF INORGANIC COMPOUNDS UNDER HYDROTHERMAL CONDITIONS

    EPA Science Inventory

    This research will utilize the high-intensity x-rays available at the Advance Photon Source (APS) to study the inorganic chemistry occurring during the hydrothermal oxidation of tank waste and the chemistry associated with tank waste vitrification. Although the chemical conversio...

  16. 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

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. [Application of ICP-AES to the chemical speciation of heavy metals in flyash].

    PubMed

    Guo, Yu-Wen; Pu, Li-Mei; Qiao, Wei; Wang, Wei; Wan, Xiao; Zhang, Xin-Rong

    2006-08-01

    Chemical speciation of seven heavy metals of flyashes in incinerator was quantitatively tested using ICP-AES. Results showed that ICP-AES procedure could carry out quick, exact and high precision experiments. RSD ratio for most detected metals was lower than 3% while few metals present a comparatively high RSD when whose content was near the detection limits. The recovery ratio was 85.7%-100.63% flyashes were found to have high content of Zn, Pb. Cd, Cu, Mn, Pb and Zn existed mostly as carbonates and were leachable, while Cr and Ni were combined to metal oxides substrates and present immobilization characteristics. PMID:17058967

  3. 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.

  4. 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

  5. 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...

  6. 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).

  7. Chemical behavior of Cu, Zn, Cd, and Pb in a eutrophic reservoir: speciation and complexation capacity.

    PubMed

    Tonietto, Alessandra Emanuele; Lombardi, Ana Teresa; Choueri, Rodrigo Brasil; Vieira, Armando Augusto Henriques

    2015-10-01

    This research aimed at evaluating cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) speciation in water samples as well as determining water quality parameters (alkalinity, chlorophyll a, chloride, conductivity, dissolved organic carbon, dissolved oxygen, inorganic carbon, nitrate, pH, total suspended solids, and water temperature) in a eutrophic reservoir. This was performed through calculation of free metal ions using the chemical equilibrium software MINEQL+ 4.61, determination of labile, dissolved, and total metal concentrations via differential pulse anodic stripping voltammetry, and determination of complexed metal by the difference between the total concentration of dissolved and labile metal. Additionally, ligand complexation capacities (CC), such as the strength of the association of metals-ligands (logK'ML) and ligand concentrations (C L) were calculated via Ruzic's linearization method. Water samples were taken in winter and summer, and the results showed that for total and dissolved metals, Zn > Cu > Pb > Cd concentration. In general, higher concentrations of Cu and Zn remained complexed with the dissolved fraction, while Pb was mostly complexed with particulate materials. Chemical equilibrium modeling (MINEQL+) showed that Zn(2+) and Cd(2+) dominated the labile species, while Cu and Pb were complexed with carbonates. Zinc was a unique metal for which a direct relation between dissolved species with labile and complexed forms was obtained. The CC for ligands indicated a higher C L for Cu, followed by Pb, Zn, and Cd in decreasing amounts. Nevertheless, the strength of the association of all metals and their respective ligands was similar. Factor analysis with principal component analysis as the extraction procedure confirmed seasonal effects on water quality parameters and metal speciation. Total, dissolved, and complexed Cu and total, dissolved, complexed, and labile Pb species were all higher in winter, whereas in summer, Zn was mostly present in the

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

    PubMed

    Tytła, Malwina; Widziewicz, Kamila; Zielewicz, Ewa

    2016-04-01

    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. PMID:26419833

  9. 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

  10. 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.

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

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.; Campbell, James A.

    1999-06-01

    In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of strontium and americium/curium in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl) aethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste tanks. The project is composed of integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metal-chelate systems. This fundamental information is then used to develop thermodynamic models, which allow the prediction of changes in chemical speciation and solubility that can occur in response to changes in tank processing conditions. In this way, we can develop new approaches that address fundamental problems in aqueous speciation and at the same time provide useful and practical information needed for tank processing.

  12. Influence of clinoptilolite rock on chemical speciation of selected heavy metals in sewage sludge.

    PubMed

    Sprynskyy, M; Kosobucki, P; Kowalkowski, T; Buszewski, B

    2007-10-22

    The chemical speciation of Cd, Cu, Pb, Cr and Ni in Torun municipal sewage sludge is investigated with addition of a natural sorbent (clinoptilolite rock). The total contents of the heavy metals in the sludge are substantially lower than the corresponding limits established by European or Polish legislation excepting nickel only. But the metals concentrations excepting lead exceed significantly the natural background (average contents in soils and in the Earth's crust) in dozens. Application of the sequential chemical extraction indicated that the metals in the sewage sludge are bound mainly (over 50%) in the residual fraction. The metals form the following order by parts of the mobile form: Ni> Cd> Cr> Cu> Pb. Addition of the clinoptilolite to the sludge leads to the metals contents fall in all four fractions of the sequential procedure. Concentrations of mobile forms of cadmium, chromium, copper and nickel decrease by 87, 64, 35 and 24%, respectively, as a result of addition of 9.09% of the clinoptilolite. The total decreases of the metals amount after 9.09% clinoptilolite addition to the sludge are around 11, 15, 25, 41 and 51% for copper, nickel, chromium, cadmium and lead, respectively. PMID:17513045

  13. Relationship between redox activity and chemical speciation of size-fractionated particulate matter

    PubMed Central

    Ntziachristos, Leonidas; Froines, John R; Cho, Arthur K; Sioutas, Constantinos

    2007-01-01

    Background Although the mechanisms of airborne particulate matter (PM) related health effects remain incompletely understood, one emerging hypothesis is that these adverse effects derive from oxidative stress, initiated by the formation of reactive oxygen species (ROS) within affected cells. Typically, ROS are formed in cells through the reduction of oxygen by biological reducing agents, with the catalytic assistance of electron transfer enzymes and redox active chemical species such as redox active organic chemicals and metals. The purpose of this study was to relate the electron transfer ability, or redox activity, of the PM samples to their content in polycyclic aromatic hydrocarbons and various inorganic species. The redox activity of the samples has been shown to correlate with the induction of the stress protein, hemeoxygenase-1. Results Size-fractionated (i.e. < 0.15; < 2.5 and 2.5 – 10 μm in diameter) ambient PM samples were collected from four different locations in the period from June 2003 to July 2005, and were chemically analyzed for elemental and organic carbon, ions, elements and trace metals and polycyclic aromatic hydrocarbons. The redox activity of the samples was evaluated by means of the dithiothreitol activity assay and was related to their chemical speciation by means of correlation analysis. Our analysis indicated a higher redox activity on a per PM mass basis for ultrafine (< 0.15 μm) particles compared to those of larger sizes. The PM redox activity was highly correlated with the organic carbon (OC) content of PM as well as the mass fractions of species such as polycyclic aromatic hydrocarbons (PAH), and selected metals. Conclusion The results of this work demonstrate the utility of the dithiothreitol assay for quantitatively assessing the redox potential of airborne particulate matter from a wide range of sources. Studies to characterize the redox activity of PM from various sources throughout the Los Angeles basin are currently

  14. Runoff rates, chemical speciation and bioavailability of copper released from naturally patinated copper.

    PubMed

    Karlén, C; Wallinder, I Odnevall; Heijerick, D; Leygraf, C

    2002-01-01

    The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building

  15. 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

  16. 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. PMID:26546228

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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

  18. 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

  19. 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.

  20. 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.

  1. Chemical Speciation of Americium, Curium and Selected Tetravalent Actinides in High Level Waste

    SciTech Connect

    Felmy, Andrew R.

    2004-06-01

    Large volumes of high-level waste (HLW) currently stored in tanks at DOE sites contain both sludges and supernatants. The sludges are composed of insoluble precipitates of actinides, radioactive fission products, and nonradioactive components. The supernatants are alkaline carbonate solutions, which can contain soluble actinides, fission products, metal ions, and high concentrations of major electrolytes including sodium hydroxide, nitrate, nitrite, phosphate, carbonate, aluminate, sulfate, and organic complexants. The organic complexants include several compounds that can form strong aqueous complexes with actinide species and fission products including ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), citrate, glycolate, gluconate, and degradation products, formate and oxalate. The goal of this project is to determine the effects of hydrolysis, carbonate complexation, and metal ion displacement on trivalent and selected tetravalent actinide speciation in the presence of organic chelates present in tank waste and to use these data to develop accurate predictive thermodynamic models for use in chemical engineering applications at Hanford and other DOE sites.

  2. 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

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

    SciTech Connect

    Nadia Ghedini; Cristina Sabbioni; Alessandra Bonazza; Giancarlo Gobbi

    2006-02-01

    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 order to 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 that the 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. 24 refs., 1 fig., 4 tabs.

  4. Chemical speciation of arsenic in the livers of higher trophic marine animals.

    PubMed

    Kubota, Reiji; Kunito, Takashi; Tanabe, Shinsuke

    2002-01-01

    Concentrations of total arsenic and individual arsenic compounds were determined in livers of cetaceans (Dall's porpoise and short-finned pilot whale), pinnipeds (harp and ringed seals), sirenian (dugong), and sea turtles (green and loggerhead turtles) to characterize arsenic accumulation profiles in higher trophic marine animals. Hepatic arsenic concentrations in sea turtles were highest among the species examined. Chemical speciation of arsenic revealed that arsenobetaine was the major arsenic compound in almost all the species. In contrast, arsenobetaine was a minor constituent in dugong. Dimethylarsinic acid, methylarsonic acid, arsenocholine, tetramethylarsonium ion, arsenite, and an unidentified arsenic compound were also detected as minor constituents. However, the composition of arsenic compounds was different among these species. These results might reflect the differences in the metabolism of arsenic and/or the compositions of arsenic compounds in their preys. To our knowledge, this is the first report on the large variation in the composition of arsenic species in liver of marine mammals and sea turtles. PMID:12398388

  5. Chemical Speciation of Trace Metals in Superficial Sediment from Lake Hongfeng, China

    NASA Astrophysics Data System (ADS)

    Hu, Jiwei; Huang, Xianfei; Zhang, Yuxia; Li, Cunxiong; Qin, Fanxin

    2010-11-01

    Heavy metals have been well known to cause numerous adverse effects to humans and ecological systems, and pollution of aquatic systems with heavy metals has aroused a huge public concern. The work reported in this paper deals with the distribution characteristics of trace metals (Pb, Cu, Zn and Ni) in ten surface sediments from Lake Hongfeng, situated in Guizhou Province of southwestern China. Apart from total concentration, the distribution of these metals in four fractions (exchangeable and weak acid soluble fraction (F1), reducible fraction (F2), oxidizable fraction (F3) and residual fraction (F4)) was also studied by means of an analytical procedure involving sequential chemical extraction that was proposed by the Commission of the European Communities Bureau of Reference (BCR). Analysis of total concentration suggested that the mean concentrations of heavy metals under study decreased in the order of Zn>Cu>Pb>Ni, and pollution of all these heavy metals in the North Lake was more serious than that in the South Lake. Study of heavy metals chemical speciation revealed that Pb and Cu were mainly distributed in reducible and residual fractions, and Zn and Ni mainly existed in residual fraction. Therefore, special attention should be paid to Pb and Cu since they presented a large fraction distributed in the exchangeable and weak acid soluble fraction and reducible fraction that were associated with high potential bioavailability. The Pearson correlation analysis between these heavy metals distributed in different fractions and some major elements were also carried out, and the results proved that sulfur (H2S) played an important role in distribution and transformation of heavy metals, especially for Pb, Cu and Zn.

  6. 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...

  7. The ToF-ACSM: a portable aerosol chemical speciation monitor with TOFMS detection

    NASA Astrophysics Data System (ADS)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Prévôt, A. S. H.; Baltensperger, U.; Schneider, J.; Kimmel, J. R.; Gonin, M.; Rohner, U.; Worsnop, D. R.; Jayne, J. T.

    2013-11-01

    We present a new instrument for monitoring aerosol composition, the time-of-flight aerosol chemical speciation monitor (ToF-ACSM), combining precision state-of-the-art time-of-flight mass spectrometry with stability, reliability, and easy handling, which are necessities for long-term monitoring operations on the scale of months to years. Based on Aerodyne aerosol mass spectrometer (AMS) technology, the ToF-ACSM provides continuous online measurements of chemical composition and mass of non-refractory submicron aerosol particles. In contrast to the larger AMS, the compact-sized and lower-priced ToF-ACSM does not feature particle sizing, similar to the widely-used quadrupole-ACSM (Q-ACSM). Compared to the Q-ACSM, the ToF-ACSM features a better mass resolution of M/ΔM = 600 and better detection limits on the order of < 30 ng m-3 for a time resolution of 30 min. With simple upgrades these limits can be brought down by another factor of ~ 8. This allows for operation at higher time resolutions and in low concentration environments. The associated software packages (single packages for integrated operation and calibration and analysis) provide a high degree of automation and remote access, minimising the need for trained personnel on site. Intercomparisons with Q-ACSM, C-ToF-AMS, nephelometer and scanning mobility particle sizer (SMPS) measurements, performed during a first long-term deployment (> 10 months) on the Jungfraujoch mountain ridge (3580 m a.s.l.) in the Swiss Alps, agree quantitatively. Additionally, the mass resolution of the ToF-ACSM is sufficient for basic mass defect resolved peak fitting of the recorded spectra, providing a data stream not accessible to the Q-ACSM. This allows for quantification of certain hydrocarbon and oxygenated fragments (e.g. C3H7+ and C2H3O+, both occurring at m/Q = 43 Th), as well as improving inorganic/organic separation.

  8. The ToF-ACSM: a portable aerosol chemical speciation monitor with TOFMS detection

    NASA Astrophysics Data System (ADS)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Prévôt, A. S. H.; Baltensperger, U.; Schneider, J.; Kimmel, J. R.; Gonin, M.; Rohner, U.; Worsnop, D. R.; Jayne, J. T.

    2013-07-01

    We present a new instrument for monitoring aerosol composition, the economy time-of-flight-aerosol chemical speciation monitor (ToF-ACSM), combining precision of state-of-the-art time-of-flight mass spectrometry with stability, reliability, and easy handling, which are necessities for long-term monitoring operations on the scale of months to years. Based on Aerodyne aerosol mass spectrometer (AMS) technology, the ToF-ACSM provides continuous online measurements of chemical composition and mass of non-refractory submicron aerosol particles. In contrast to the larger AMS, the compact-sized and lower-priced ToF-ACSM does not feature particle sizing, similar to the widely-used quadrupole-ACSM (Q-ACSM). Compared to the Q-ACSM, the ToF-ACSM features a better mass resolution of M/ΔM = 600 and better detection limits on the order of <30 ng m-3 for a time resolution of 30 min. With simple upgrades these limits can be brought down by another factor of ~8. This allows for operation at higher time resolutions and in low concentration environments. The associated software packages (single packages for integrated operation & calibration and analysis) provide a high degree of automation and remote access, minimising the need for trained personnel on site. Intercomparisons with Q-ACSM, C-ToF-AMS, nephelometer and scanning mobility particle sizer (SMPS) measurements, performed during a first long-term deployment (>6 months) on the Jungfraujoch mountain ridge (3580 m a.s.l.) in the Swiss Alps agree quantitatively. Additionally, the mass resolution of the ToF-ACSM is sufficient for basic mass defect resolved peak fitting of the recorded spectra, providing a data stream not accessible to the Q-ACSM. This allows for quantification of certain hydrocarbon and oxygenated fragments (e.g. C3H7+ and C2H3O+, both occurring at m/Q = 43 Th), as well as improving inorganic/organic separation.

  9. Questions concerning environmental mobility of arsenic: needs for a chemical data base and means for speciation of trace organoarsenicals.

    PubMed

    Brinckman, F E; Parris, G E; Blair, W R; Jewett, K L; Iverson, W P; Bellama, J M

    1977-08-01

    Biomethylation of metals, including arsenic, apparently occurs as a global process. Health control strategies therefore depend on accurate analysis of arsenic's environmental mobility. Determining to what extent biotransformations occur and how resultant organometal(loids) are sequestered in food chains requires sophistication beyond present-day total element determinations. Rather, active molecular forms of arsenic must be speciated for each environmental compartment, and it is necessary to quantify the dynamics of arsenic's mobility. Thus, new chemical facts are needed yielding rates of methylation or demethylation of arsenic; partition coefficients of organoarsenicals between air, water, and organic phases; and arsenic redox chemistry in polar media. NBS research in this context is reviewed with examples of recent results emphasizing speciation methodology. Topic areas discussed are: the nature of aquated methylarsenic species (NMR and laser-Raman spectroscopy); transport of methylarsenicals from aqueous media (gas chromatography-graphic furnace AA detection applied to metabolic Me3As formation); and speciation of involatile organoarsenicals in aqueous media (demonstration of HPLC utilizing element-specific AA detection and appraisal of electrochemical detectors). PMID:908286

  10. 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.

  11. 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.

  12. Prediction of chemical speciation in stabilized/solidified wastes using a general chemical equilibrium model. 2: Doped waste contaminants in cement porewaters

    SciTech Connect

    Park, J.Y.; Batchelor, B.

    1999-01-01

    In the previous paper, SOLTEQ demonstrated its ability to represent chemical speciation in the pure s/s binder systems. The objective of this paper is to provide a method for representing doped waste contaminants in SOLTEQ so that their speciation can be determined. To evaluate this method, model predictions were compared with measured concentrations in the porewaters expressed from cement pastes doped with various metal salts. Among doped metals, only mercury showed concentrations that indicated primary control by precipitation. The other metals, such as Cr(VI), Cd, Pb, and Na, showed behaviors that imply sorption as a major immobilization mechanism. The Langmuir isotherm was found to be well suited to describe the sorption of Na{sup +} ions onto the effective surface of CSH. To support the sorption of metal anions onto presumably negatively charged silica surface in cement porewater, a hypothesis of super-equivalent adsorption is proposed.

  13. 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).

  14. 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

  15. 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

  16. 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

  17. The concentration and chemical speciation of arsenic in the Nanpan River, the upstream of the Pearl River, China.

    PubMed

    Yang, Silin; Zhao, Ning; Zhou, Dequn; Wei, Rong; Yang, Bin; Pan, Bo

    2016-04-01

    The concentration and chemical speciation of arsenic (As) in different environmental matrixes (water, sediment, agricultural soils, and non-agricultural soils) were investigated in the Nanpan River area, the upstream of Pearl River, China. The results did not show any obvious transport of As along the flow direction of the river (from upstream to downstream). Total As concentrations in sediment were significantly different from those in agricultural soil. According to the comparison to quality standards, the As in sediments of the studied area have potential ecological risks and a minority of the sampling sites of agricultural soils in the studied area were polluted with As. As speciations were analyzed using sequential extraction and the percentage of non-residual fraction in sediment predominated over residual fraction. We thus believe that As in the studied area was with low mobility and bioavailability in sediment, agricultural soils, and non-agricultural soils. However, the bioavailability and mobility of As in sediment were higher than in both agricultural and non-agricultural soils, and thus, special attention should be paid for the risk assessment of As in the river in future studies. PMID:26627697

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Chemical speciation and bioavailability of selenium in the rhizosphere of Symphyotrichum eatonii from reclaimed mine soils.

    PubMed

    Oram, Libbie L; Strawn, Daniel G; Möller, Gregory

    2011-02-01

    Knowledge of rhizosphere influences on Se speciation and bioavailability is required to predict Se bioavailability to plants. In the present study, plant-availability of Se to aster (Symphyotrichum eatonii (A. Gray) G.L. Nesom) was compared in rhizosphere soils and nonrhizosphere (bulk) soils collected from a reclaimed mine site in southeastern Idaho, U.S. X-ray spectroscopy was used to characterize the oxidation state and elemental distribution of Se in aster roots, rhizosphere soils, and bulk soils. Percent extractable Se in aster rhizosphere soil was greater than extractable Se in corresponding bulk soils in all samples (n = 4, p = 0.042, 0.051, and 0.052 for three extractions). Selenium oxidation state mapping of 28 regions within the samples and X-ray absorption near edge structure (XANES) spectra from 26 points within the samples indicated that the rhizosphere and bulk soil Se species was predominantly reduced Se(-II,0), while in the aster roots, high concentrations of Se(VI) were present. Results show that within the rhizosphere, enhanced Se bioavailability is occurring via oxidation of reduced soil Se to more soluble Se(VI) species. PMID:21166454

  3. Comparison of the spectroscopic speciation and chemical fractionation of chromium in contaminated paddy soils.

    PubMed

    Hsu, Liang-Ching; Liu, Yu-Ting; Tzou, Yu-Min

    2015-10-15

    Sequential extraction has been widely used to classify metal species in soils and sediments; however, the lack of selectivity in extraction reagents may lead to the misinterpretation of metal speciation. In this study, we used X-ray absorption near edge structure (XANES) spectroscopy to classify Cr species based on its molecular form. These results complement the conventional Cr fractionation derived from the Tessier extraction method. The linear combination fitting (LCF) for the Cr-XANES spectra indicated that the Cr species in the soils could generally be described as Cr(III) sorbed on ferrihydrite (Cr-FH), Cr(III) complexed with humic acid (Cr-HA), and precipitated Cr. While the sum of the adsorbed Cr(III) and Cr(III)/Fe coprecipitates showed a nearly 1:1 relationship with reducible Cr, the total of Cr precipitates and organic Cr also followed the same trend with oxidizable Cr. This result indicated that there might be a underestimation in the reducible fraction as pure Cr(III) precipitates associated with surfaces of Fe minerals would not be extracted in the reducible process. Instead, such pure Cr(III) precipitates were dissolved during the oxidizable process, resulting in a overestimation in the fractionation of organic-related Cr. PMID:25935296

  4. 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. PMID:24238918

  5. Internal iron biomineralization in Imperata cylindrica, a perennial grass: chemical composition, speciation and plant localization.

    PubMed

    Rodríguez, N; Menéndez, N; Tornero, J; Amils, R; de la Fuente, V

    2005-03-01

    * The analysis of metal distribution in Imperata cylindrica, a perennial grass isolated from the banks of Tinto River (Iberian Pyritic Belt), an extreme acidic environment with high content in metals, has shown a remarkable accumulation of iron. This property has been used to study iron speciation and its distribution among different tissues and structures of the plant. * Mossbauer (MS) and X-ray diffraction (XRD) were used to determine the iron species, scanning electron microscopy (SEM) to locate iron biominerals among plant tissue structures, and energy-dispersive X-ray microanalysis (EDAX), X-ray fluorescence (TXRF) and inductively coupled plasma emission spectroscopy (ICP-MS) to confirm their elemental composition. * The MS spectral analysis indicated that iron accumulated in this plant mainly as jarosite and ferritin. The presence of jarosite was confirmed by XRD and the distribution of both minerals in structures of different tissues was ascertained by SEM-EDAX analysis. * The convergent results obtained by complementary techniques suggest a complex iron management system in I. cylindrica, probably as a consequence of the environmental conditions of its habitat. PMID:15720689

  6. Development of Fundamental Data on Chemical Speciation and Solubility for Strontium and Americium in High Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.; Campbell, James A.

    2000-06-01

    In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2- hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high level waste tanks. The project is comprised of integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metal-chelate systems. This fundamental information is then used to develop thermodynamic models which allows the prediction of changes in chemical speciation and solubility which can occur in response to changes in tank processing conditions. In this way we can both develop new approaches that address fundamental problems in aqueous speciation and at the same time provide useful and practical information needed for tank processing.

  7. Development of Fundamental Data on Chemical Speciation and Solubility for Strontium and Americium in High- Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.

    2001-06-01

    In this research program, Pacific Northwest National Laboratory and Florida State University are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid [EDTA], N-(2-hydroxyethyl)ethylenediaminetriacetic acid [HEDTA], nitrilotriacetic acid [NTA], iminodiacetic acid [IDA], citrate, and oxalate) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste stored in tanks at Hanford and other U.S. Department of Energy (DOE) sites. The project comprises integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metalchelate systems. This fundamental information then is used to develop thermodynamic models designed to predict changes in chemical speciation and solubility resulting from various tank processing conditions. In this way we can develop new approaches that address fundamental problems in aqueous speciation and, at the same time, provide useful and practical information needed for tank waste processing.

  8. 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

  9. 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

  10. 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

  11. Development of Fundamental Data on Chemical Speciation and Solubility for Strontium and Americium in High-Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.

    2002-06-01

    In this project, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste (HLW) stored in tanks at Hanford and other U.S. Department of Energy (DOE) sites. The chelating agents that are being studied are EDTA (ethylenediaminetetraacetic acid), HEDTA (N-(2-hydroxyethyl)ethylenediaminetriacetic acid), NTA (nitrilotriacetic acid), IDA (iminodiacetic acid), citrate, and oxalate. The project comprises integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metalchelate systems. This fundamental information then is used to develop thermodynamic models designed to predict changes in chemical speciation and solubility resulting from various tank processing conditions. In this way we can develop new approaches that address fundamental problems in aqueous speciation and, at the same time, provide useful and practical information needed for tank waste processing. Current strategies for reducing the total volume of radioactive tank waste requiring disposal at Hanford and other DOE sites call for the development of methods that can be used to selectively dissolve and remove non-radioactive elements, such as Al, P, and Cr, while retaining or precipitating the radioactive elements, including Sr and the actinide elements, in the tank sludge. This partitioning between solids and precipitates is fundamentally dependent on the chemical speciation of the elements present in the tank processing solutions. Of particular importance is separation of the radioactive and

  12. 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

  13. [Physical-chemical characteristics and phosphorus speciation of the sediments in the upper and middle reaches of the Yellow River].

    PubMed

    Wang, Xiao-Li; Bao, Hua-Ying; Guo, Bo-Shu

    2009-03-15

    The physical and chemical characteristics, various phosphorus forms from 10 sites in Yellow River's sediments were analyzed, and their relations were discussed. The results showed that, the values of total phosphorus, organic matter and active Fe, Al are 97.86-129.33 mg x kg(-1), 0.11%-1.96%, 2.02-7.40 mg x g(-1), 0.29-0.90 mg x g(-1), respectively. The main mineral compositions of the sediments are quartz and albite; the main clay minerals are montmorillonate, illite, chlorite and kaolinite. Inorganic-P is the main form of phosphorus speciation. Ca-P is 37.61-64.04 mg x kg(-1) and is the main form of IP. The cation exchange capacity was linearly correlated with the sum of clay and silt (R2 = 0.76). Also, the organic matter was linearly correlated with inorganic sedimentary phosphorus (R2 = 0.66). Moreover, the linear relationship between the sum of NaOH-P and BD-P and the sum of active Fe and active Al content was observed within the ten sediments investigated (R2 = 0.80). PMID:19432318

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. Numerical Simulation of the Transport and Speciation of Nonconservative Chemical Reactants in Rivers

    NASA Astrophysics Data System (ADS)

    Chapman, Bernard M.

    1982-02-01

    A computer model, previously used to simulate the transport of conservative chemical components in streams, has been used as a basis for a more complex model which includes the effects due to processes such as precipitation and sedimentation and adsorption onto stationary reactive surfaces which render the reactants nonconservative with respect to the flowing waters. The model uses, as before, the program MINEQL as a basis for the chemical equilibrium submodel. The physical transport submodel employs a convolution integral procedure, with an approximate form of the impulse function to solve a one-dimensional convective-diffusion equation. Although the model essentially assumes chemical equilibrium, a pseudokinetic treatment is necessary to deal with redissolution of precipitates and dissociation of surface species. Simple hypothetical examples are given to illustrate the operation of the model. The model is then applied to an experiment in which the base NaOH is injected into a creek draining an abandoned base metal mine. Concentrations of the metals Zn, Al, Cu, Fe, and Na in the flowing waters, expressed in terms of total metals and as suspended solids, are followed as a function of time and distance downstream. Significant sedimentation of the precipitates formed is evident, and the existence of substantial quantities of protons and/or metal ions, adsorbed on the streambed, is implied from the model calculations. The model was able to simulate successfully the major features observed. This simulation involved the simultaneous formation of five distinct precipitates and one surface species.

  19. Efficient chemical equilibrium calculations for geochemical speciation and reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Blunt, Martin J.; LaForce, Tara C.

    2014-04-01

    Chemical equilibrium calculations are essential for many environmental problems. It is also a fundamental tool for chemical kinetics and reactive transport modelling, since these applications may require hundreds to billions equilibrium calculations in a single simulation. Therefore, an equilibrium method for such critical applications must be very efficient, robust and accurate. In this work we demonstrate the potential effectiveness of a novel Gibbs energy minimisation algorithm for reactive transport simulations. The algorithm includes strategies to converge from poor initial guesses; capabilities to specify non-linear equilibrium constraints such as pH of an aqueous solution and activity or fugacity of a species; a rigorous phase stability test to determine the unstable phases; and a strategy to boost the convergence speed of the calculations to quadratic rates, requiring only few iterations to converge. We use this equilibrium method to solve geochemical problems relevant to carbon storage in saline aquifers, where aqueous, gaseous and minerals phases are present. The problems are formulated to mimic the ones found in kinetics and transport simulations, where a sequence of equilibrium calculations are performed, each one using the previous solution as the initial guess. The efficiency and convergence rates of the calculations are presented, which require an average of 1-2 iterations. These results indicate that critical applications such as chemical kinetics and reactive transport modelling can potentially benefit by using this multiphase equilibrium algorithm.

  20. Single Particle Chemical Speciation of Ambient Ultrafine Particulate Matter in Atlanta, GA

    NASA Astrophysics Data System (ADS)

    Sipin, M. F.; Su, Y.; Prather, K. A.

    2002-12-01

    Ultrafine particles, particles with aerodynamic diameters lower than 100 nm, have recently gained increasing attention because of their hypothesized adverse heath effects and potential as cloud condensation nuclei. Chemical characterization of the ultrafine particles at the single particle level is important for assessing their impact on human health and understanding their formation and behavior. This is beneficial for modeling studies and regulations on pollution control. In August 2002, continuous ambient monitoring was performed in an industrial area in Atlanta, GA. Characterization of the urban particulate matter with aerodynamic diameters 30A›ƒ,ªƒ_o300 nm was carried out using a dual polarity aerosol time-of-flight mass spectrometer (ATOFMS) interfaced with an aerodynamic lens system. This configuration allows on-line real time simultaneous acquisition of size and chemical information for individual particles down to 30 nm. The ultrafine particles observed consisted of elemental carbon (EC), organic carbon (OC), and a mixture of OC and EC as a result of vehicular, industrial, and biogenic emissions. These major particle types, their associations with inorganics (i.e. ammonium, sulfate, nitrate, potassium, calcium, and metal oxides), and their temporal and size variations will be presented.

  1. Chemical speciation of strontium, americium, and curium in high level waste: Predictive modeling of phase partitioning during tank processing. 1998 annual progress report

    SciTech Connect

    Felmy, A.R.

    1998-06-01

    'In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high level waste tanks. The fundamental understanding of chemical speciation reactions gained from these studies is also used to propose methodologies for removal of Sr and Am/Cm from organic chelates present in high level tank waste, via competition, displacement or other reactions, without the need for the development of costly and potentially hazardous organic destruction technologies.'

  2. Chemical speciation of strontium, americium, and curium in high-level waste: Predictive modeling of phase partitioning during tank processing. 1997 annual progress report

    SciTech Connect

    Felmy, A.R.; Choppin, G.R.

    1997-06-01

    'In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, and ionic strength conditions present in high-level waste tanks. This fundamental understanding of chemical speciation reactions is essential to develop methodologies for removal of Sr and Am/Cm from the chelates, via competition, displacement or other reactions, without the need for the development of costly and potentially hazardous organic destruction technologies. These studies specifically focus on the effects of hydrolysis, carbonate concentration, ionic strength, and selected cation competition on the removal of Sr and Am/Cm from the organic chelates.'

  3. 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

  4. Chemical speciation and source apportionment of Non-Methane Volatile Organic Compounds (NMVOCs) in a Middle Eastern country

    NASA Astrophysics Data System (ADS)

    Salameh, Therese; Sauvage, Stéphane; Afif, Charbel; Borbon, Agnès; Locoge, Nadine

    2014-05-01

    NMVOCs, emitted from various sources, are of particular interest since they contribute to the formation of tropospheric ozone, PAN and secondary organic aerosols resulting in negative impacts on human health, climate and on the environment. To identify abatement measures, a profound knowledge of emission sources and their composition is a prerequisite. Air pollution in the Middle East region remains difficult to assess and understand because of a lack of ground-based measurements and the limited information on NMVOC chemical speciation and source apportionment. Based on a large database of NMVOC observations obtained in Beirut, the capital of Lebanon (a developing country in the Middle East region, located in Western Asia on the eastern shore of the Mediterranean Sea), the overall objective of this work is to apportion the sources of NMVOCs encountered in Lebanon. First, source profiles were determined with field measurements close to the main potential emitters namely the road transport, gasoline vapour, power generation and solvent uses. The results obtained are compared to other studies held in other regions and are used to assess the emission inventory developed for Lebanon. Secondly, two intensive field campaigns were held in a receptor site in Beirut during summer 2011 and winter 2012 in order to obtain a large time resolved dataset. The PMF analysis of this dataset was applied to apportion anthropogenic sources in this area. In both seasons, combustion (road transport and power generation) and gasoline evaporation, especially in winter, were the main sources contributing to the NMVOCs in Beirut. The results will support model implementation especially by completing the emission inventory established for the year 2010 by Waked et al. 2012 according to the EEA/EMEP guidelines because of the lack of Lebanon-specific emission factor.

  5. 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.

  6. 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

  7. 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.

  8. 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.

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

    DOE PAGESBeta

    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

  10. Chemical speciation in laser-desorption and impact-induced vapor in minerals

    NASA Astrophysics Data System (ADS)

    Shen, A. H.; Dundas, C. M.; Ahrens, T. J.; Beauchamp, J. L.

    2002-12-01

    Knowledge of the chemical species in vapors produced by hypervelocity impact on spacecraft impact detectors as well as planetary surfaces have applications ranging from determination of the composition of cosmic dust to the effects on atmospheres and climates of large impactors. Direct study of resulting atomic, molecular and ionic species is best accomplished via mass spectrometry. Pulsed laser desorption can be used to approximate small impacts on solid surfaces. We conducted pulsed laser desorption-ionization experiments using two different instruments: (1) a Caltech-built Time-of-Flight Mass Spectrometer (TOFMS) similar to that on board the Cassini spacecraft and (2) a commercial Matrix Assisted Laser Desorption Ionization TOFMS made by Applied Biosystems (Model, Voyager-DE Pro). Minerals included in this study were calcite, dolomite, gypsum, anhydrite, olivine, kamacite, brucite, serpentine, and pyrrhotite. We collected only positive ions. A nitrogen laser (337 nm wavelength, 4 μsec pulse width, and 300 mJ) with power density ranging from 1.0x107 to 1.3x109 W/cm2 induced vaporization and ionization. The results can be summarized as: (1) from kamacite and pyrrhotite, only 54Fe+, 56Fe+, 57Fe+ (both kamacite and pyrrhotite) and 58Ni+, 60Ni+ (kamacite only) as well as contamination ions such as 23Na+ and 39K+, 41K+were observed; (2) Ca-containing minerals (calcite, dolomite, gypsum and anhydrite) produced vapors containing 40Ca+ ions, and, at higher laser power, both 40Ca+ as well as CaO+ ions; (3) Mg-containing minerals (dolomite, olivine, brucite and serpentine) produced vapors containing MgO+ ion; (4) for all hydrous minerals, neither H+ nor H3O+ were observed in the vapor; (5) in the vapors of silicate minerals (olivine and serpentine), SiO+ was observed only from serpentine but not from olivine.

  11. 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

  12. 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.

  13. Ion Current Rectification in Nano/Micro-Fluidic Interfaces and Pulsed Glow Discharge Time-of-Flight Mass Spectrometric Chemical Speciation

    NASA Astrophysics Data System (ADS)

    Wang, Han

    Microfluidics continues to be of interest for analyzing chemical and biological samples because of the disposability, portability, low sample consumption, fast analysis time, and parallel analysis potential for multiple samples in a single device. To improve microfluidic device functionality, integrated systems-nanofluidic/microfluidic interfaces (NMIs) have been fabricated for concentrating samples and performing as molecular gates. Ion current rectification has been confirmed in NMI with an asymmetric system. In chapter 2, the asymmetry of the NMI is systematically altered by varying the inner diameter of the nanocapillary membrane (NCM) reservoir, and the current rectification factor is observed to increase as the inner diameter of NCM reservoir increases. The data provide a new approach to tune the ion current rectification of NMIs and strengthen the fundamental knowledge of how these devices function. Glow discharge mass spectrometry (GDMS) is a well-established technique for the direct analysis of elements in solid samples. The introduction of pulsed glow discharge makes the internal energy of GD plasma tunable so that the specific desired ion signal profiles can be obtained and used for chemical speciation. For example, the elemental, structural, and molecular information of organic molecules have been obtained nearly simultaneously using glow discharge time-of-flight mass spectrometry (GDToFMS) coupled with gas chromatography. With careful control of operating parameters of GDToFMS, specific cluster ions or ion abundance ratios can be used for speciation of chromium oxides, manganese oxides, and iron oxides. Chapters 3 and 4 focus on extending the application of pulsed glow discharge time-of-flight mass spectrometry for chemical speciation. Chapter 3 is the analysis of cysteine using pulsed glow discharge time-of-flight mass spectrometry. The characteristic fragment ion at m/z 76 is used for the quantitative analysis for cysteine. The calibration curve for

  14. 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

  15. 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.

  16. 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…

  17. 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. PMID:24727132

  18. Storm water runoff measurements of copper from a naturally patinated roof and from a parking space. Aspects on environmental fate and chemical speciation.

    PubMed

    Odnevall Wallinder, I; Hedberg, Y; Dromberg, P

    2009-12-01

    Release of copper from a naturally aged copper roof on a shopping centre building in a suburban site of Stockholm has been measured during different rain events after its interaction with the internal drainage system and storm drains made of cast iron and concrete. Concentrations of copper removed by means of urban storm water from a nearby parking space have been determined for comparison. Predictions and measurements of the chemical speciation of released copper are discussed compared to the total concentration, and to threshold values for freshwater and drinking water. The results clearly illustrate that the major part of the released copper from the roof is readily retained already during transport through the internal drainage system of the building, a pathway that also changes the chemical speciation of released copper and its bioavailable fraction. Most copper, not retained by cast iron and concrete surfaces, was strongly complexed to organic matter. The median concentration of free cupric ions and weak copper complexes was less than, or within the range of reported no effect concentrations, NOECs, of copper in surface waters. The parking space contributed with significantly higher and time-dependent concentrations of total copper compared to measured concentrations of copper from the roof after the interaction with the drainage system. Most copper in the surface runoff water was strongly complexed with organic matter, hence reducing the bioavailable fraction significantly to concentrations within the NOEC range. Dilution with other sources of urban storm water will reduce the released concentration of copper even further. The results illustrate that already the internal drainage system and the storm drains made of cast iron and concrete act as efficient sinks for released copper which means that any installation of additional infiltration devices is redundant. PMID:19762062

  19. 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. PMID:23126560

  20. 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.

  1. Chemical speciation of dissolved Cu, Ni, and Co in a contaminated estuary in southwest Spain and its influence on plankton communities.

    PubMed

    Braungardt, Charlotte B; Achterberg, Eric P; Gledhill, Martha; Nimmo, Malcolm; Elbaz-Poulichet, Francoise; Cruzado, Antonio; Velasquez, Zoila

    2007-06-15

    Four surveys of the Huelva Estuary in southwest Spain and its sources, the Tinto and the Odiel Rivers, were carried out between 1996 and 1998. The surveys investigated the impact of metalliferous mining of sulfide-rich ores in the catchment area on metal speciation, metal concentrations in a macrophyte, and phytoplankton diversity and abundance. Chemical speciation measurements in the lower Tinto Estuary showed that metals were predominantly electrochemically labile (> 99% of total dissolved Cu, Co, and Ni at 10 microM Cu, 424 nM Co, and 500 nM Ni, S = 28). Concentrations of Cu complexing ligands and free cupric ions [Cu2+] in the Gulf of Cádiz ranged between 5.3 and 38 nM and 0.2-7.9 pM, respectively, with conditional stability constants of the ligands of log K'(CuL) = 11.7-12.6. At enhanced dissolved Cu concentrations in the lower Huelva Estuary, Cu complexing ligands were saturated with Cu, resulting in nanomolar [Cu2+], which increased upstream. Metal tissue concentrations of the macrophyte Blindingia marginata were high, and a clear relationship between dissolved labile Cu and macrophyte tissue Cu concentrations was observed. A low biodiversity was observed in the Huelva system (Shannon-Wiener indices (H) typically < 0.2). Nevertheless, the maximum biomass was observed in the lower Tinto Estuary, which showed high labile metal and nutrient concentrations and a low biodiversity (H < 0.02), thereby suggesting adaptation through evolutionary processes of the phytoplankton community to the harsh conditions. PMID:17626415

  2. 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

  3. 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

  4. 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.

  5. Canadian National Air Pollution Surveillance (NAPS) PM 2.5 speciation program: Methodology and PM 2.5 chemical composition for the years 2003-2008

    NASA Astrophysics Data System (ADS)

    Dabek-Zlotorzynska, Ewa; Dann, Tom F.; Kalyani Martinelango, P.; Celo, Valbona; Brook, Jeffrey R.; Mathieu, David; Ding, Luyi; Austin, Claire C.

    2011-01-01

    The Canadian National Air Pollution Surveillance (NAPS) network, monitoring criteria gases (CO, O 3, NO x, and SO 2), PM 2.5, PM 10, volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and particle chemical mass and composition, has been in operation for over 40 years. Since 1984 both fine (<2.5 μm - PM 2.5) and coarse (2.5-10 μm - PM 10-2.5) particle mass measurements have been made at NAPS network sites using dichotomous samplers. In January 2003, the NAPS PM 2.5 speciation program was initiated with the purpose of measuring all major components of PM 2.5, including ammonium nitrate, ammonium sulphate, metals, and organic and elemental carbon. The present paper describes the improved sampling (e.g. Teflon/Nylon filter packs for nitrate loss, and an active blank for each and every sample in the determination of positive organic carbon artifacts), and analytical methods used in the Canadian NAPS PM 2.5 speciation program. A detailed dataset was then analyzed for seasonal and geographical variations in the major components of 24-h time integrated PM 2.5 samples collected at eight urban and three rural measurement sites across Canada (2003-2008). Chemical mass reconstruction was used for assessment of the adequacy of selected sampling and chemical parameters as well as for the determination of the relative contributions of different compound classes to PM 2.5 mass. The highest frequency of PM 2.5 episodes exceeding 30 μg m -3 were observed in Ontario and southern Quebec. In general, the most important contributions to PM 2.5 mass were secondary aerosol sulphate and nitrate (38-63% for western sites and 3-44% for eastern sites), depending on the season. Organic matter (OM) was found to be the second most important component (21-45%), while particle-bound water (PBW) accounted for 6-12% of the PM 2.5 mass. Golden B.C. was an exception, exhibiting high levels of OM (60-70%) and low levels of PBW (˜3%).

  6. 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

  7. 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

  8. 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.

  9. A PERSONAL PARTICLE SPECIATION SAMPLER

    EPA Science Inventory

    Dr. Susanne Hering of Aerosol Dynamics Inc and her colleagues expect to design and validate a personal monitoring sampler for particles smaller than 2.5 µm (PM2.5) that is suitable for subsequent chemical speciation work. The investigators believe the result will be a...

  10. 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.

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

    SciTech Connect

    Hopkins, Rebecca J; Desyaterik, Yury; Tivanski, Alexei V; Zaveri, Rahul A; Berkowitz, Carl M; Tyliszczak, T; Gilles, Marry K; Laskin, Alexander

    2008-02-27

    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 complementary combination of 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 (TOFSIMS), 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 an air mass 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 the characteristic ratios of CH3SO3-/nss-SO42-> 0.6. Although this value seems too high for a mid-latitude site, our model calculations suggest that high CH3SO3-/nss-SO42- ratios are expected during the early stages of dimethyl sulfide (DMS) oxidation when CH3SO3H forms more rapidly than H2SO4.

  12. Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors.

    PubMed

    Shakeri Yekta, Sepehr; Gustavsson, Jenny; Svensson, Bo H; Skyllberg, Ulf

    2012-01-30

    The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (≈ 60% of total S) and reduced organic S (≈ 30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed. PMID:22284519

  13. Molybdenum X-ray absorption edges from 200 to 20,000eV: the benefits of soft X-ray spectroscopy for chemical speciation.

    PubMed

    George, Simon J; Drury, Owen B; Fu, Juxia; Friedrich, Stephan; Doonan, Christian J; George, Graham N; White, Jonathan M; Young, Charles G; Cramer, Stephen P

    2009-02-01

    We have surveyed the chemical utility of the near-edge structure of molybdenum X-ray absorption edges from the hard X-ray K-edge at 20,000eV down to the soft X-ray M(4,5)-edges at approximately 230eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO(4)(2-) and MoS(4)(2-). We used three criteria for assessing near-edge structure of each edge: (i) the ratio of the observed chemical shift between MoO(4)(2-) and MoS(4)(2-) and the linewidth, (ii) the chemical information from analysis of the near-edge structure and (iii) the ease of measurement using fluorescence detection. Not surprisingly, the K-edge was by far the easiest to measure, but it contained the least information. The L(2,3)-edges, although harder to measure, had benefits with regard to selection rules and chemical speciation in that they had both a greater chemical shift as well as detailed lineshapes which could be theoretically analyzed in terms of Mo ligand field, symmetry, and covalency. The soft X-ray M(2,3)-edges were perhaps the least useful, in that they were difficult to measure using fluorescence detection and had very similar information content to the corresponding L(2,3)-edges. Interestingly, the soft X-ray, low energy ( approximately 230eV) M(4,5)-edges had greatest potential chemical sensitivity and using our high-resolution superconducting tunnel junction (STJ) fluorescence detector they appear to be straightforward to measure. The spectra were amenable to analysis using both the TT-multiplet approach and FEFF. The results using FEFF indicate that the sharp near-edge peaks arise from 3d-->5p transitions, while the broad edge structure has predominately 3d-->4f character. A proper understanding of the dependence of these soft X-ray spectra on ligand field and site geometry is necessary before a complete assessment of the utility of the Mo M(4,5)-edges can be made. This work includes crystallographic characterization of sodium tetrathiomolybdate. PMID:19041140

  14. Molybdenum X-Ray Absorption Edges from 200 – 20,000 eV, The Benefits of Soft X-Ray Spectroscopy for Chemical Speciation

    PubMed Central

    George, Simon J.; Drury, Owen B.; Fu, Juxia; Friedrich, Stephan; Doonan, Christian J.; George, Graham N.; White, Jonathan M.; Young, Charles G.; Cramer, Stephen P.

    2009-01-01

    We have surveyed the chemical utility of the near-edge structure of molybdenum x-ray absorption edges from the hard x-ray K-edge at 20,000 eV down to the soft x-ray M4,5-edges at ~230 eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO4 and MoS42-. We used three criteria for assessing near-edge structure of each edge: (i) the ratio of the observed chemical shift between MoO42- and MoS42- and the linewidth, (ii) the chemical information from analysis of the near-edge structure and (iii) the ease of measurement using fluorescence detection. Not surprisingly, the K-edge was by far the easiest to measure, but it contained the least information. The L2,3-edges, although harder to measure, had benefits with regard to selection rules and chemical speciation in that they had both a greater chemical shift as well as detailed lineshapes which could be theoretically analyzed in terms of Mo ligand field, symmetry, and covalency. The soft x-ray M2,3-edges were perhaps the least useful, in that they were difficult to measure using fluorescence detection and had very similar information content to the corresponding L2,3-edges. Interestingly, the soft x-ray, low energy (~230 eV) M4,5-edges had greatest potential chemical sensitivity and using our high resolution superconducting tunnel junction (STJ) fluorescence detector they appear to be straightforward to measure. The spectra were amenable to analysis using both the TT-multiplet approach and FEFF. The results using FEFF indicate that the sharp near-edge peaks arise from 3d → 5p transitions, while the broad edge structure has predominately 3d → 4f character. A proper understanding of the dependence of these soft x-ray spectra on ligand field and site geometry is necessary before a complete assessment of the utility of the Mo M4,5-edges can be made. This work includes crystallographic characterization of sodium tetrathiomolybdate. PMID:19041140

  15. pH-metric chemical speciation modeling and studies of in vitro antidiabetic effects of bis[(imidazolyl)carboxylato]oxidovanadium(IV) complexes.

    PubMed

    Gundhla, Isaac Z; Walmsley, Ryan S; Ugirinema, Vital; Mnonopi, Nandipha O; Hosten, Eric; Betz, Richard; Frost, Carminita L; Tshentu, Zenixole R

    2015-04-01

    A range of bidentate N,O-donor ligands of the imidazolyl-carboxylate moiety, which partially mimic naturally occurring bioligands, were prepared and reacted with the oxidovanadium(IV) ion to form the corresponding bis-coordinated oxidovanadium(IV) complexes. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry, which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave evidence that the bis[(imidazolyl)carboxylato]oxovanadium(IV) complexes possess a broad pH-metric stability. The complexes improved glucose uptake in cell cultures using 3T3-L1 adipocytes, C2C12 muscle cells and Chang liver cells. The PTP inhibition studies indicated that the mechanism underlying insulin-stimulated glucose uptake was possibly via the protein tyrosine phosphorylation through the inhibition of the protein tyrosine phosphatase 1B (PTP 1B). The vanadium compounds also demonstrated the inhibition of D-dimer formation, suggesting that these compounds could potentially relieve a hypercoagulative state in diabetic patients. PMID:25594947

  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. 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.

  18. 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).

  19. 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.

  20. 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.

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

    DOE PAGESBeta

    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

  2. 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.

  3. Chemical speciation and source apportionment of gaseous precursors observed at a remote site in the Mediterranean basin

    NASA Astrophysics Data System (ADS)

    Michoud, Vincent; Sauvage, Stéphane; Dusanter, Sébastien; Leonardis, Thierry; Locoge, Nadine

    2014-05-01

    Models of atmospheric chemistry suggest that aged anthropogenic air masses still contain significant levels of reactive trace gases such as mono- and multi-functional oxygenated volatile organic compounds, even after several days of oxidation. These air masses can significantly impact the oxidative capacity and the formation rate of secondary pollutants (ozone, SOA…) at remote locations. However, large uncertainties still remain about chemical processes occurring during long range transport that leads to the oxidation of anthropogenic pollutants. Long term measurements of volatile organic compounds and inorganic species are being conducted since July 2012 at a remote site in Cape Corsica, a receptor site experiencing events of long range transport of air masses from different urbanized areas (south of France, Spain, Italia, North of Africa). In addition to the long term monitoring, an extended suite of trace gases and aerosols was acquired as part of the 2013 ChArMEx field campaign at Cape Corsica. One of the objectives was to better understand chemical and physical processes occurring during long range transport of anthropogenic plumes. In this presentation, we will first apportion primary and secondary sources of VOCs observed at this remote site using an analysis of spatial and temporal variations of their concentrations, ratios of chemical tracers, and air mass trajectory clustering. We will then present the results from a concentration field approach. This statistical method, based on a large set of data, consists in redistributing the concentrations of selected VOCs to the trajectories in order to identify potential source areas influencing the receptor site. The results of these two approaches will provide relevant information to study chemical processes occurring in different types of plumes transported over the Mediterranean basin.

  4. PROGRESS REPORT. DEVELOPMENT OF FUNDAMENTAL DATA ON CHEMICAL SPECIATION AND SOLUBILITY FOR STRONTIUM AND AMERICIUM IN HIGH-LEVEL WASTE: PREDICTIVE MODELING OF PHASE PARTITIONING DURING TANK PROCESSING

    EPA Science Inventory

    In this research program, Pacific Northwest National Laboratory and Florida State University are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid [EDTA], N-(2-hydroxyethyl)ethylenediaminetriacetic a...

  5. 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

  6. 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

  7. 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.

    1994-12-31

    XANES (X-ray Absorption Near Edge Spectroscopy) has been employed to evaluate the efficacy of a process designed to encapsulate and reduce TcO{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 TcO{sub 4}{sup {minus}}. 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. The first investigation was to evaluate the effectiveness of a chemical reaction designed to slow the release of {sup 99}TcO{sub 4}{sup {minus}} in nuclear wasteform cements. The second investigation was to characterize the oxidation state of Se after microbial uptake from an aqueous solution by common soil bacteria, in order to provide information about the possible mechanisms of bioremediation.

  8. 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...

  9. 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.

  10. 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.

  11. 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. PMID:19465717

  12. 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.

  13. 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 ...

  14. 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.

  15. 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. PMID:25341186

  16. 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.

  17. Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model

    SciTech Connect

    Dooley, S.; Burke, M. P.; Chaos, M.; Stein, Y.; Dryer, F. L.; Zhukov, V. P.; Finch, O.; Simmie, J. M.; Curran, H. J.

    2010-07-16

    The oxidation of methyl formate (CH{sub 3}OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions: 1. A variable-pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K. 2. Shock tube ignition delays have been determined for CH{sub 3}OCHO/O{sub 2}/Ar mixtures at pressures of ≈ 2.7, 5.4, and 9.2 atm and temperatures of 1275–1935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0). 3. Laminar burning velocities of outwardly propagating spherical CH{sub 3}OCHO/air flames have been determined for stoichiometries ranging from 0.8–1.6, at atmospheric pressure using a pressure-release-type high-pressure chamber. A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbon monoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to depend on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments.

  18. 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

  19. ANNUAL REPORT. DEVELOPMENT OF FUNDAMENTAL DATA ON CHEMICAL SPECIATION AND SOLUBILITY FOR STRONTIUM AND AMERICIUM IN HIGH LEVEL WASTE: PREDICTIVE MODELING OF PHASE PARTITIONING DURING TANK PROCESSING

    EPA Science Inventory

    In this project, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents over ranges of hydroxide, carbonate, ionic strength, and competing metal ion conc...

  20. 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

  1. 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

  2. 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

  3. Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Kirpichtchikova, Tatiana A.; Manceau, Alain; Spadini, Lorenzo; Panfili, Fré; dé; ric; Marcus, Matthew A.; Jacquet, Thierry

    2006-05-01

    that one of the three predominant Zn species was highly soluble under the extraction conditions. Comparison of EXAFS data before and after chemical treatment revealed that the Zn phosphate component was entirely and selectively dissolved in the first 24 h of contact time. Preferential dissolution of the Zn phosphate component is supported by thermodynamic calculations. Despite the long-term contamination of this soil, about 79% of Zn, 91% of Pb, and 100% of Cu can be solubilized in the laboratory on a time scale of a few days by chemical complexants. According to metal speciation results and thermodynamic calculations, the lower extraction level measured for Zn is due to the Zn phyllosilicate component, which is less soluble than Zn phosphate and Zn ferrihydrite.

  4. 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

  5. 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

  6. 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...

  7. Chemical Composition of Semivolatile Compounds and Organic Aerosol in a Pine Forest: Bulk and Speciated Measurements by In-situ TAG-AMS and Offline GCxGC/HRTOFMS at BEACHON-RoMBAS 2011

    NASA Astrophysics Data System (ADS)

    Chan, A. W.; Kreisberg, N. M.; Zhao, Y.; Hohaus, T.; Campuzano Jost, P.; Teng, A.; Huang, I.; Jayne, J.; Worsnop, D. R.; Jimenez, J. L.; Hering, S. V.; Goldstein, A. H.

    2012-12-01

    Semivolatile organic compounds (SVOCs) represent an important source of organic aerosol (OA) in remote forested regions. Understanding their composition is essential to identifying their sources and processing, but the chemical complexity often limits such analysis. Here we present concurrent bulk and speciated measurements of semivolatile and particle-phase organic compounds using a novel combined instrument (TAG-AMS) at Manitou Forest, CO during the BEACHON-RoMBAS 2011 campaign. The Thermal desorption Aerosol Gas chromatograph (TAG) provides on-line organic speciation of ambient SVOCs with bihourly time resolution, while the AMS provides bulk mass spectral analysis of the concurrent OA sample. This deployment was a unique and experimental version of the TAG-AMS instrument, with a prototype filter cell designed to quantitatively collect and analyze SVOCs. The combined instrument provides quantitative measurements of organic and inorganic mass loadings, and elemental and PMF analysis of the bulk OA, simultaneously with detailed organic speciation of SVOCs. Additionally, filter samples are analyzed by comprehensive GCxGC/HR-TOF-MS to assist in compound identification by TAG. The system provided around-the-clock measurements for a 2-week period. Online and offline measurements reveal > 100 compounds, a subset of which is observed at a bihourly time resolution, and is used to identify the sources of organic aerosol in the region. Bihourly measurements of sesquiterpenes, which represent a major fraction of observed SVOCs, are used to investigate their emission sources and subsequent processing into OA. These observations are also compared to a previous study conducted at a similar pine forest in California.

  8. 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...

  9. 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.

  10. 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...

  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. 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

  13. 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.'

  14. 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.

  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. 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

  19. Adsorption of Cr(VI) and Speciation of Cr(VI) and Cr(III) in Aqueous Solutions Using Chemically Modified Chitosan

    PubMed Central

    Dai, Jun; Ren, FengLian; Tao, ChunYuan

    2012-01-01

    A new type of grafting chitosan (CTS) was synthesized using 2-hydroxyethyl- trimethyl ammonium chloride (HGCTS). The adsorption of Cr(VI) on HGCTS was studied. The effect factors on adsorption and the adsorption mechanism were considered. The results indicated that the HGCTS could concentrate and separate Cr(VI) at pH 4.0; the adsorption equilibrium time was 80 min; the maximum adsorption capacity was 205 mg/g. The adsorption isotherm and kinetics were investigated, equilibrium data agreed very well with the Langmuir model and the pseudo second-order model could describe the adsorption process better than the pseudo first-order model. A novel method for speciation of Cr(VI) and Cr(III) in environmental water samples has been developed using HGCTS as adsorbent and FAAS as determination means. The detection limit of this method was 20 ng/L, the relatively standard deviation was 1.2% and the recovery was 99%~105%. PMID:22754471

  20. Distribution, chemical speciation, and mobility of lead and antimony originating from small arms ammunition in a coarse-grained unsaturated surface sand.

    PubMed

    Lewis, Jeffrey; Sjöström, Jan; Skyllberg, Ulf; Hägglund, Lars

    2010-01-01

    This study quantified the heavy metal contamination caused by firing 500 high-velocity 7.62-mm jacketed Swedish military rounds. Contamination of solid and aqueous phases was studied, with Pb and Sb being the two contaminants of primary interest. The distribution of the Pb and Sb were measured in terms of depth of penetration in sand and grain size distribution of the bullet particles. The Pb- and Sb-contaminated sand was then used as a source material in two bench-scale unsaturated lysimeters to measure the transport of Pb and Sb through two coarse-grained sands, which were taken from the berms on two Swedish military small arms ranges. The lysimeters were subjected to an infiltration cycle that reproduced spring snowmelt, which is the most significant infiltration event of the year in northern climates. The levels of mobile Pb and Sb were monitored in the effluent from the lysimeters. Extended X-ray absorption fine-structure spectroscopy analysis was performed on the contaminated sands to determine Pb speciation before and after leaching. Ninety-three percent of the mass of bullets was found in the top 30 cm of sand. Lead oxide was the predominant species of Pb before and after leaching. Transport of Pb was small, with aqueous concentrations remaining stable at <2 microg L(-1). Antimony was far more mobile, with solute breakthrough occurring between 5 and 14 d and concentrations rising to over 125 microg L(-1) within 1 month. PMID:20400582

  1. PM2.5 speciation -- objectives, requirements, and approach

    SciTech Connect

    Homolya, J.B.; Rice, J.; Scheffe, R.D.

    1998-12-31

    Chemical speciation of selected PM2.5 monitor samples is included in the discussion of major monitoring requirements and principles described in the Part 58 Rule. The regulation requires the implementation of a modest chemical speciation network of 50 PM2.5 sites that provides a first order characterization of the metals, ions, and carbon constituents of PM2.5. These data are to be used to support several areas of interest, including: (1) Helping to implement the PM2.5 standard through the use of speciated data as inputs to air quality modeling analyses and as indicators to track progress of controls; (2) Aiding the interpretation of health studies by linking effects to PM2.5 constituents; (3) Understanding the effects of atmospheric constituents on visibility impairment; and (4) Using speciated particulate data to aid in monitoring network design and siting adjustment. For these reasons, EPA has developed plans for the initial 50-site speciation monitoring network that include collocating at least 25 monitors within the Photochemical Air Monitoring System (PAMS) which collect data for a range of volatile hazardous air pollutants and ozone. Therefore these initial speciation sites will provide EPA and the research community a baseline of gaseous and particulate atmospheric characterization information. Current plans include the outfitting of up to 300 PM2.5 speciation monitoring sites. The speciation monitors are currently being fabricated under EPA National Federal Reference Method monitor procurement contracts and are projected to begin to be deployed in 10/98. This paper will present a detailed discussion of the design and implementation of the speciation monitoring network and explain EPA`s approach to implementation of the monitoring activities which includes siting, target analytes of interest, sample handling, analytical SOPs, and data reduction, validation and reporting.

  2. 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 ...

  3. 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

  4. 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.

  5. Evaluation of a pulsed glow discharge time-of-flight mass spectrometer as a detector for gas chromatography and the influence of the glow discharge source parameters on the information volume in chemical speciation analysis.

    PubMed

    Fliegel, Daniel; Fuhrer, Katrin; Gonin, Marc; Günther, Detlef

    2006-09-01

    The figures of merit of a pulsed glow discharge time-of-flight mass spectrometer (GD-TOFMS) as a detector for gas chromatography (GC) analysis were evaluated. The mass resolution for the GD-TOFMS was determined on FWHM in the high mass range (208Pb+) as high as 5,500. Precision of 400 subsequent analyses was calculated on 63Cu+ to be better than 1% RSD with no significant drift over the time of the analysis. Isotope precision based on the 63Cu+/65Cu+ ratio over 400 analyses was 1.5% RSD. The limits of detection for gaseous analytes (toluene in methanol as solvent) were determined to be as low as several hundred ppb or several hundred pg absolute without using any pre-concentration technique. Furthermore, the different GD source parameters like capillary distance, cathode-anode spacing, and GD source pressure with regards to the accessible elemental, structural, and molecular information were evaluated. It was demonstrated that each of these parameters has severe influence on the ratio of elemental, structural, and parent molecular information in chemical speciation analysis. PMID:16773303

  6. 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.

  7. 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

  8. Chemical Speciation of Water Soluble Ions and Metals of Cloud and Rain Water During the Puerto Rico African Dust and Clouds Study (PRADACS) Campaigns

    NASA Astrophysics Data System (ADS)

    Torres, E.; Valle Diaz, C. J.; Lee, T.; Collett, J. L.; Fitzgerald, E.; Cuadra-Rodriguez, L. A.; Prather, K. A.; Sánchez, M.; McDowell, W. H.; Mayol-Bracero, O. L.

    2013-05-01

    The underlying physico-chemical processes of dust particles interactions are poorly understood; even less understood is how aging impacts cloud properties and climate as the particles travel from Africa to the Caribbean region. Caribbean landmasses have tropical montane cloud forests (TMCFs) that are tightly coupled to the atmospheric hydrologic cycle. TMCFs are ecosystems to study the effects African Dust (AD) on cloud formation and precipitation as these are very sensitive ecosystems that respond to small changes in climate. As part of the Puerto Rico African Dust and Clouds Study (PRADACS), chemical analyses were performed on cloud and rain water samples collected at Pico del Este (PE) station in Luquillo, PR (1051 masl) during campaigns held from 2010 to 2012. At PE, two cloud collectors (i.e., single stage (Aluminum version), a 2-stage (Teflon version) Caltech Active Strand Cloudwater Collector (CASCC)), a rainwater collector, and anAerosol Time-Of-Flight Mass Spectrometer (ATOFMS) were operated. Chemical analyses performed on collected samples include pH, conductivity, ion chromatography (IC), and inductive coupled plasma (ICP). Results from these campaigns showed that on days that had air masses with the influence of AD, cloud water samples had higher conductivity and pH values on average (up to 5.7 and 180μS/cm, respectively) than those with air masses without AD influence. An increase in the concentrations of water-soluble ions like non-sea salt calcium and magnesium, and metals like magnesium, calcium and aluminum was observed and the appearance of iron was seen on ICP analyses. The ATOFMS, showed an increase on the amount of particles during AD influence with composition of aluminum, silicates, potassium, iron and titanium aerosols. The increase on the aforementioned species was constant in the three years of sampling, which give us confidence in the identification of the chemical species that are present during the influence of AD.

  9. Oxidation-state speciation of

    PubMed

    Hu; Heineman

    2000-06-01

    The analytical utility of chemically modified microelectrodes for oxidation-state speciation of redox couples by cyclic voltammetry has been explored. [Re(I)(DMPE)3]+/[Re(II)(DMPE)3]2+, where DMPE = 1,2-bis(dimethylphosphino)ethane, was studied at carbon-fiber microelectrodes of approximately 5 microm in radius coated with Nafion-entrapped solgel-derived silica (Nafion-silica) composite. The results are compared with cyclic voltammetry of [Fe(CN)6]3-/[Fe(CN)6]4- at bare carbon-fiber microelectrodes. At both microelectrodes, the cathodic and anodic limiting currents are linearly proportional to the concentrations of the reducible and oxidizable species of a redox couple, respectively. The shape of the cyclic voltammogram and the magnitude of the steady-state limiting current are not affected by the potential at which the scan starts. Speciation of both forms of a redox couple could be achieved voltammetrically at the microelectrodes. However, a considerably slower scan rate was required to achieve steady state at the modified electrode because of the smaller diffusion coefficients of [Re(I)(DMPE)3]+ and [Re(II)(DMPE)3]2+ in the Nafion-silica composite. The detection limit at the modified electrode was considerably lower (5 x 10(-9) M for [Re(I)(DMPE)3]+) than at the bare electrode (6 x 10(-5) M for [Fe(CN)6]3- and [Fe(CN)6]4-) because of the substantial preconcentration of [Re(I)(DMPE)3]+ by the Nafion-silica composite. PMID:10857611

  10. Flow injection method for the rapid determination of chemical oxygen demand based on microwave digestion and chromium speciation in flame atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Cuesta, A.; Todoli, J. L.; Canals, A.

    1996-12-01

    The present paper describes a new flow injection method for the determination of Chemical Oxygen Demand (COD). This method consists of a first digestion step, where the sample is heated by microwave radiation, a second one where an anionic exchange resin retains the Cr(VI) that has not been reduced by the organic matter of the sample and a third one where Cr(VI), after being eluted, is determined by flame atomic absorption spectrometry. The microwave power applied, the sulphuric acid concentration, the liquid flow in the digestion step and the sample volume were the variables studied. The recovery and precision obtained with this method are similar to those obtained using a standard semi-micro method, whereas the throughput is much higher (up to 50 determinations per hour). As regards sensitivity, by changing the sample loop volume and the concentration of dichromate, one can analyze samples with Chemical Oxygen Demand values between 25 and 5000 mg/l. The limit of detection is about 7 mg/l COD. An interesting feature of the new method, which is not shared by most other flow injection methods of Chemical Oxygen Demand determination, is that there is no matrix effect in the determination step.

  11. 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. PMID:23258765

  12. 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. ...

  13. 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

  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. 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

  16. Chemical speciation at buried interfaces in high-temperature processed polycrystalline silicon thin-film solar cells on ZnO:Al

    NASA Astrophysics Data System (ADS)

    Becker, Christiane; Pagels, Marcel; Zachäus, Carolin; Pollakowski, Beatrix; Beckhoff, Burkhard; Kanngießer, Birgit; Rech, Bernd

    2013-01-01

    The combination of polycrystalline silicon (poly-Si) thin films with aluminum doped zinc oxide layers (ZnO:Al) as transparent conductive oxide enables the design of appealing optoelectronic devices at low costs, namely in the field of photovoltaics. The fabrication of both thin-film materials requires high-temperature treatments, which are highly desired for obtaining a high electrical material quality. Annealing procedures are typically applied during crystallization and defect-healing processes for silicon and can boost the carrier mobility and conductivity of ZnO:Al layers. In a combined poly-Si/ZnO:Al layer system, an in-depth knowledge of the interaction of both layers and the control of interface reactions upon thermal treatments is crucial. Therefore, we analyze the influence of rapid thermal treatments up to 1050 °C on solid phase crystallized poly-Si thin-film solar cells on ZnO:Al-coated glass, focusing on chemical interface reactions and modifications of the poly-Si absorber material quality. The presence of a ZnO:Al layer in the solar cell stack was found to limit the poly-Si solar cell performance with open circuit voltages only below 390 mV (compared to 435 mV without ZnO film), even if a silicon nitride (SiN) diffusion barrier was included. A considerable amount of diffused zinc inside the silicon was observed. By grazing-incidence X-ray fluorescence spectrometry, a depth-resolving analysis of the elemental composition close to the poly-Si/(SiN)/ZnO:Al interface was carried out. Temperatures above 1000 °C were found to promote the formation of new chemical compounds within about 10 nm of interface, such as zinc silicates (Zn2SiO4) and aluminium oxide (AlxOy). These results give valuable insights about the temperature-limitations of Si/ZnO thin-film solar cell fabrication and the formation of high-mobility ZnO-layers by thermal anneal.

  17. [Analysis of chemical speciation of heavy metals in L07-11 profile sediments of "Big Ear" Region of Lop Nor Lake].

    PubMed

    Zhu, Xin-ping; Zhang, Liang-hui; Jiang, Ping-an; Jia, Hong-tao; Zheng, Chun-xia; Fan, Shun-hui

    2014-12-01

    As playa is the typical characteristic in "Big Ear" Region of Lop Nor Lake, it is significant for enriching playa heavy metal earth environmental chemical data by analyzing species distribution of heavy metal among this district. In this thesis, heavy metal Cd, Pb, Ni, Cu in L07-11 Profile Sediments of "Big Ears" Region of Lop Nor Lake are considered as research objects. Tessier sequential extraction and Graphite furnace atomic absorption method (GF-990) are used to discuss and analyze five forms of Cd, Pb, Ni, Cu among sediments. The results show that the content of Cd, Pb, Ni and Cu is in the range from 1.10~2.54, 9.18~20.02, 9.88~17.15, 4.43~21.11 mg · kg(-1), respectively. The value of organic matter range from 8.71-54.72 g · kg(-1). The order of the bioavailable state in heavy metals is Cd>Pb>Cu>Ni. Pb and Cd mainly exist in exchangeable form including water-soluble, and that Ni is in residual form, and that Cu is mostly in Fe-Mn oxide bound iron-manganese oxides or in residual form. Among surface sediments, effective content of heavy metal is more than 80%. Except Cu, the content of heavy metal Cd, Pb, Ni in exchangeable form is more than 60%. Heavy metal Cd and Pb has higher secondary release potential. The content of heavy metal and organic material has some correlation. PMID:25881435

  18. 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

  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 185ppm/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 5.2ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5ppm) 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. 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 ...

  1. 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.

  2. 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...

  3. 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).

  4. 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...

  5. 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

  6. 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.

  7. 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

  8. 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

  9. Arabidopsis hybrid speciation processes

    PubMed Central

    Schmickl, Roswitha; Koch, Marcus A.

    2011-01-01

    The genus Arabidopsis provides a unique opportunity to study fundamental biological questions in plant sciences using the diploid model species Arabidopsis thaliana and Arabidopsis lyrata. However, only a few studies have focused on introgression and hybrid speciation in Arabidopsis, although polyploidy is a common phenomenon within this genus. More recently, there is growing evidence of significant gene flow between the various Arabidopsis species. So far, we know Arabidopsis suecica and Arabidopsis kamchatica as fully stabilized allopolyploid species. Both species evolved during Pleistocene glaciation and deglaciation cycles in Fennoscandinavia and the amphi-Beringian region, respectively. These hybrid studies were conducted either on a phylogeographic scale or reconstructed experimentally in the laboratory. In our study we focus at a regional and population level. Our research area is located in the foothills of the eastern Austrian Alps, where two Arabidopsis species, Arabidopsis arenosa and A. lyrata ssp. petraea, are sympatrically distributed. Our hypothesis of genetic introgression, migration, and adaptation to the changing environment during the Pleistocene has been confirmed: We observed significant, mainly unidirectional gene flow between the two species, which has given rise to the tetraploid A. lyrata. This cytotype was able to escape from the narrow ecological niche occupied by diploid A. lyrata ssp. petraea on limestone outcrops by migrating northward into siliceous areas, leaving behind a trail of genetic differentiation. PMID:21825128

  10. 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.

  11. 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.

  12. Cancer: beyond speciation.

    PubMed

    Vincent, Mark D

    2011-01-01

    A good account of the nature of cancer should provide not only a description of its consistent features, but also how they arise, how they are maintained, why conventional chemotherapy succeeds, and fails, and where to look for better targets. Cancer was once regarded as enigmatic and inexplicable; more recently, the "mutation theory," based on random alterations in a relatively small set of proto-oncogenes and tumor suppressor genes, has enjoyed widespread acceptance. The "mutation theory," however, is noticeable for its failure to explain the basis of differential chemosensitivity, for providing a paucity of targets, especially druggable ones, and for justifying the development of targeted therapies with, in general, disappointingly abbreviated clinical benefit. Furthermore, this theory has mistakenly predicted a widespread commonality of consistent genetic abnormalities across the range of cancers, whereas the opposite, that is, roiling macrogenomic instability, is generally the rule. In contrast, concerning what actually is consistent, that is, the suite of metabolic derangements common to virtually all, especially aggressive, cancers, the "Mutation Theory" has nothing to say. Other hypotheses merit serious consideration "aneuploidy theories" posit whole-genome instability and imbalance as causally responsible for the propagation of the tumor. Another approach, that is, "derepression atavism," suggests cancer results from the release of an ancient survival program, characterized by the emergence of remarkably primitive features such as unicellularity, fermentation, and immortality; existential goals are served by heuristic genomic instability coupled with host-to-tumor biomass interconversion, mediated by the Warburg effect, a major component of the program. Carcinogenesis is here seen as a process of de-speciation; however, genomic nonrestabilization raises issues as to where on the tree of life cancers belong, as a genuinely alternative modus vivendi

  13. 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

  14. PASSENGER CAR HYDROCARBON EMISSIONS SPECIATION

    EPA Science Inventory

    Emission factors for over 60 individual hydrocarbon compounds were determined for four passenger cars. The cars included a 1963 Chevrolet, a 1977 Mustang, and 1978 Monarch, and 1979 LTD II. The speciation data is reported for both tailpipe and evaporative emissions. The tailpipe ...

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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...

  20. Lead Speciation in remote Mountain Lakes

    NASA Astrophysics Data System (ADS)

    Plöger, A.; van den Berg, C. M. G.

    2003-04-01

    In natural waters trace metals can become complexed by organic matter. This complexation can change the geochemistry of the metals by preventing them being scavenged, thereby increasing their residence time in the water column. The chemical speciation of trace metals also affects the bioavalability and their toxicological impact on organisms. It is therefore important to determine the chemical speciation of trace metals as well as their concentrations. Mountain lakes have been less studied in the past than other lakes- partly because of their remoteness and partly because they were perceived to be unpolluted and undisturbed. But work so far on mountain lakes has shown that most sites are affected and threatened, for example by transboundary air pollutants like trace metals. One of the important features that distinguishes these lakes from lowland lakes at similar latitudes is the fact that they may be isolated from the atmosphere for six months or more during the winter by a thick ice cover. Also, as these lakes are remote from direct anthropogenic influences, they reflect the regional distribution of pollutants transferred via the atmosphere. For this work, under the framework of the EMERGE (European Mountain lake Ecosystems: Regionalisation, diaGnostic and socio-economic Evaluation) programme, two remote mountain lakes have been studied in detail, with water sampling taking place at different times of the year to investigate possible seasonal differences in lead concentrations and speciation. Results so far have shown that lead-complexing ligand concentrations are in excess to dissolved lead concentrations, indicating that dissolved lead probably occurs fully complexed in these lakes. Therefore the toxic fraction is likely to be less than the dissolved lead concentration. Also, lead concentrations at the time of the spring thaw are higher than autumn concentrations just before ice cover, indicating that a significant proportion of fallout onto the lake catchment

  1. Role of natural nanoparticles on the speciation of Ni in andosols of la Reunion

    NASA Astrophysics Data System (ADS)

    Levard, Clément; Doelsch, Emmanuel; Rose, Jérôme; Masion, Armand; Basile-Doelsch, Isabelle; Proux, Olivier; Hazemann, Jean-Louis; Borschneck, Daniel; Bottero, Jean-Yves

    2009-08-01

    Andosols on the island of Réunion have high nickel (Ni) concentrations due to the natural pedo-geochemical background. Enhanced knowledge of Ni speciation is necessary to predict the bioavailability and potential toxicity of this element. Ni speciation in these andosols, marked by the presence of high amounts of natural aluminosilicate nanoparticles, was investigated in two complementary systems: (i) In a soil sample—densimetric fractionation was first performed in order to separate the potential bearing phases, prior to Ni speciation characterization. (ii) In a synthetic sample—Ni reactivity with synthetic aluminosilicate nanoparticle analogs were studied. In both cases, Ni speciation was determined using X-ray absorption spectroscopy (XAS). The results revealed that Ni had the same local environment in both systems (natural and synthetic systems), and Ni was chemically linked to natural short-range ordered aluminosilicates or analogs. This complex represented about 75% of the total Ni in the studied soil.

  2. 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 ...

  3. 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...

  4. Possible method for dissolved organic carbon speciation in forest soils

    NASA Astrophysics Data System (ADS)

    Drabek, O.; Tejnecký, V.; Ash, C.; Hubova, P.; Boruvka, L.

    2013-12-01

    Dissolved organic carbon (DOC) is a natural part of dissolved organic matter and it plays an important role in the biogeochemistry of soil processes. Low Molecular Mass Organic Acids (LMMOA) are an essential part of DOC. These acids play a key role in chemical processes that affect the entire soil environment. Knowing the amount of DOC and the speciation of LMMOA is required for realistic equilibrium modelling of soil chemical processes and transport mechanisms. There have been a number of proposed methods for the quantitative analysis of DOC and for speciation of LMMOA. The first aim of this contribution is to introduce and test a modified spectroscopic method for the determination of water-extractable organic carbon (WEOC) from forest soils. In general this method is based on the oxidization of WEOC by chromium-sulphuric acid. The presented method can be used as an economical alternative to the classical, more financially demanding elemental analysis. However, the main aim is to test the reliability of the method for LMMOA speciation. Ion exchange chromatography (IC) with hydroxide elution has proven to be a useful tool for the determination of LMMOA in many different water-based samples. However, the influence of multivalent cations (often present in environmental samples) on IC results has not yet been sufficiently studied. In order to assess the influence of Al, Fe, Mn, Mg and Ca on the amount of LMMOA determined by IC, an extensive set of model solutions was prepared and immediately analysed by means of IC. Moreover, the influence of pH on determined amounts of LMMOA in model solutions and representative soil aqueous extracts was investigated. These experimental results were compared to expected values and also to results provided by the chemical equilibrium model - PHREEQC. Based on the above listed research, some modifications to the common IC method for LMMOA speciation are presented.

  5. Coal liquefaction process streams characterization and evaluation: The use of selective chemical reactions and carbon NMR spectroscopy in the speciation and quantification of oxygen functional groups in coal resids

    SciTech Connect

    Stock, L.M.; Cheng, C.

    1992-11-01

    This study demonstrated the feasibility of using phase-transfer methylation reactions for the derivatization of hydroxyl functionalities and single-electron transfer reactions to cleave ether groups in distillation resid materials derived from direct coal liquefaction. {sup 13}C-NMR was used to analyze the reaction products. It was demonstrated that the techniques can be used to speciate and quantify about half of the oxygen in resids. The remaining half of the oxygen is presumed to be present as unreactive ethers, probably dibenzofurans. Hydroxyl concentrations were determined on five resid samples and ether cleavage reactions were conducted on three of those five. Further development of this general analytical strategy as a process development tool is justified based on these results.

  6. Coal liquefaction process streams characterization and evaluation: The use of selective chemical reactions and carbon NMR spectroscopy in the speciation and quantification of oxygen functional groups in coal resids

    SciTech Connect

    Stock, L.M.; Cheng, C. . Dept. of Chemistry)

    1992-11-01

    This study demonstrated the feasibility of using phase-transfer methylation reactions for the derivatization of hydroxyl functionalities and single-electron transfer reactions to cleave ether groups in distillation resid materials derived from direct coal liquefaction. [sup 13]C-NMR was used to analyze the reaction products. It was demonstrated that the techniques can be used to speciate and quantify about half of the oxygen in resids. The remaining half of the oxygen is presumed to be present as unreactive ethers, probably dibenzofurans. Hydroxyl concentrations were determined on five resid samples and ether cleavage reactions were conducted on three of those five. Further development of this general analytical strategy as a process development tool is justified based on these results.

  7. 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...

  8. 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

  9. 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.

  10. On the scent of speciation: the chemosensory system and its role in premating isolation.

    PubMed

    Smadja, C; Butlin, R K

    2009-01-01

    Chemosensory speciation is characterized by the evolution of barriers to genetic exchange that involve chemosensory systems and chemical signals. Here, we review some representative studies documenting chemosensory speciation in an attempt to evaluate the importance and the different aspects of the process in nature and to gain insights into the genetic basis and the evolutionary mechanisms of chemosensory trait divergence. Although most studies of chemosensory speciation concern sexual isolation mediated by pheromone divergence, especially in Drosophila and moth species, other chemically based behaviours (habitat choice, pollinator attraction) can also play an important role in speciation and are likely to do so in a wide range of invertebrate and vertebrate species. Adaptive divergence of chemosensory traits in response to factors such as pollinators, hosts and conspecifics commonly drives the evolution of chemical prezygotic barriers. Although the genetic basis of chemosensory speciation remains largely unknown, genomic approaches to chemosensory gene families and to enzymes involved in biosynthetic pathways of signal compounds now provide new opportunities to dissect the genetic basis of these complex traits and of their divergence among taxa. PMID:18685572

  11. Geochemical Speciation Mass Transfer

    SciTech Connect

    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 mineral 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.

  12. Geochemical Speciation Mass Transfer

    Energy Science and Technology Software Center (ESTSC)

    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

  13. 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.

  14. Investigation of DGT as a metal speciation tool in artificial human gastrointestinal fluids.

    PubMed

    Pelfrêne, Aurélie; Waterlot, Christophe; Douay, Francis

    2011-08-12

    This paper reports the results of an investigation on the performance of the diffusive gradient in thin film technique (DGT) as a speciation tool for trace elements (TEs) in artificial human gastrointestinal fluids. The validity of Cd, Pb, and Zn sampling by DGT in digestive fluids was checked. The TE bioaccessibility in highly contaminated soils was determined using the in vitro Unified Barge Method (UBM) test. DGT devices were deployed in the gastrointestinal solutions obtained after carrying out the UBM test. The computer speciation code JESS (Joint Expert Speciation System) was used to predict the metal speciation of Cd, Pb, and Zn. Combining the in vitro test with the DGT technique and JESS provided an approach to the TE species available for transport across the intestinal epithelium. The gastrointestinal absorption of ingested TE ranged from 8 to 30% for Cd, 0.6 to 11% for Pb, and 0.8 to 7% for Zn and was influenced by TE speciation. In this original approach, the DGT technique was found to be simple and reliable in the investigation of TE chemical speciation in digestive fluids. Extrapolation to the in vivo situation should be undertaken very cautiously and requires further investigation. PMID:21704772

  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. SPECIATION OF ELEMENTS IN INCINERATION RESIDUES

    EPA Science Inventory

    Knowledge as to the speciation of elements in incineration residues is important for the successful management and utilization of the residues and for modelling and predicting their leaching behavior. s part of a larger research effort on speciation in combustion residues, ESP as...

  18. Rapid speciation and chromosomal evolution in mammals.

    PubMed Central

    Bush, G L; Case, S M; Wilson, A C; Patton, J L

    1977-01-01

    To test the hypothesis that population subdivision into small demes promotes both rapid speciation and evolutionary changes in gene arrangement by inbreeding and drift, we estimated rates of speciation and rates of chromosomal evolution in 225 genera of vertebrates. Rates of speciation were estimated by considering the number of living species in each genus and the fossil record of each genus as well as information about extinction rates. Speciation rate was strongly correlated with rate of chromosomal evolution and average rates of speciation in lower vertebrate genera were one-fifth those in mammalian genera. Genera with high karyotypic diversity and rapid speciation rates may generally have small effective population size (Ne), whereas large Ne values may be associated with karyotypically uniform genera and slow rates of speciation. Speciation and chromosomal evolution seem fastest in those genera with species organized into clans or harems (e.g., some primates and horses) or with limited adult vagility and juvenile dispersal, patchy distribution, and strong individual territoriality (e.g., some rodents). This is consistent with the above hypothesis regarding the evolutionary importance of demes. PMID:269445

  19. 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 ...

  20. 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

  1. 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.

  2. The speciation of behavior analysis

    PubMed Central

    Rider, David P.

    1991-01-01

    The relationship between the Experimental Analysis of Behavior (EAB) and Applied Behavior Analysis (ABA) has been the subject of several editorials and commentaries in recent years. Various authors have argued that researchers in these two fields (a) have become isolated from each other, (b) face different requirements for survival in their respective fields, and (c) possess different skills to meet those requirements. The present paper provides an allegory for the relationship between EAB and ABA in terms of biological speciation. The conditions that have changed the relationship between EAB and ABA are parallel to those responsible for biological speciation: (a) isolation of some members of a species from the rest of the population, (b) different contingencies of survival for members of the two separate groups, and (c) divergence in the adaptive characteristics displayed by the two groups. When members of two different groups, descendants of common ancestors, no longer are capable of producing viable offspring by interbreeding, the different groups then represent different species. To the extent that members of the EAB group and members of the ABA group interact with each other only trivially, they each represent allegorically different species. Changes in the relationship between EAB and ABA are part of a natural process that takes place in many other sciences, and the course of that process can hardly be reversed by us. PMID:22478096

  3. 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, vola...

  4. 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...

  5. 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

  6. 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

  7. Iron speciation and its biological availability in seawater: A workshop

    SciTech Connect

    Wells, M.L.; Bruland, K.W.

    1995-09-08

    This workshop brought together marine chemists with expertise in iron chemistry and biologists with expertise in the role of iron in phytoplankton production to discuss controversies regarding the role of iron in oceanic primary productivity and global climatic change. A new paradigm for marine iron biogeochemistry was generated. The five major new items within this paradigm included (1) the nature of iron inputs to the sea, (2) chemical speciation of iron in seawater, (3) relationships between iron chemistry and marine microbial community dynamics, (4) adaptations of marine microbes to iron input, and (5) ecological and biogeochemical implications of changes in iron supply to the sea.

  8. 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.

  9. 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...

  10. An equilibrium analysis to determine the speciation of metals in an incinerator

    SciTech Connect

    Wu, C.Y.; Biswas, P. )

    1993-04-01

    An equilibrium analysis is carried out to determine the speciation of metals among their various forms in an incinerator. The Gibbs free energy of the system is minimized by the method of element chemical potentials combined with atom population constraints using a thermodynamic equilibrium computer code. Ninety-one compounds of six metallic species-arsenic, cadmium, chromium, lead, mercury, and tin-are analyzed in this study. The effect of temperature and chlorine content on the speciation is established. The effect of combustion of hydrocarbon fuels on the equilibrium calculation is also evaluated.

  11. 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.

  12. Zn Speciation in two Fe-Mn Banded Systems

    NASA Astrophysics Data System (ADS)

    Marcus, M.; Manceau, A.; Kersten, M.; Tazaki, K.

    2002-12-01

    We have used micro-EXAFS spectroscopy to study the speciation of Zn in two shallow-water Fe-Mn banded structures. One of the samples is from the Baltic Sea and contains anthropogenic Zn in a matrix which is believed to be banded due to annual oscillations in oxygen content, pH and other variables of water chemistry (Hlawatsch, et. al., 2002). The other sample, from Akayu Hot Springs off the coast of a volcanic island (Satsuma-Iwo Jima) at the southern tip of Japan, is a hardened biomat in which the compositional oscillations are at least partly due to bacterial action, and in which the Zn content is natural (Tazaki, 2000). By using a beam as small as 5μm in diameter, we can look at details of metal distribution and speciation on a spatial scale much finer than the banding, which has wavelengths of order 100μm. In both samples, the Zn is associated with the high-Mn layers, though the layer-to-layer contrast is lower in the Japan sample. However, the speciation of Zn is different in the two samples. The Baltic sample shows Zn only in one form - sorbed on a layered phyllomanganate resembling birnessite with Zn tetrahedrally coordinated and sorbed to vacant octahedral sites of the Mn layer. This species was also found in soil (Manceau et. al., 2000). The Japan sample also has tetrahedral Zn in birnessite-like phyllomanganate as well as Zn in at least two other forms. The phyllomanganate species is thus seen to be a ubiquitous sink for Zn in the environment. We will discuss some possible reasons for the differences and similarities of Zn speciation in these two systems. Hlawatsch, S., Garbe-Schönberg, C.D., Lechtenberg, F., Manceau, A., Tamura, N., Kulik, D.A., Kersten, M. (2002) Trace metal fluxes to ferromanganese nodules from the western Baltic Sea as a record for long-term environmental changes. Chemical Geology, 182 697-709. Manceau A., Lanson B., Schlegel M.L., Hargé J.C., Musso M., Eybert-Bérard L., Hazemann J.L., Chateigner D., Lamble G.M. (2000

  13. Chromosomes, conflict, and epigenetics: chromosomal speciation revisited.

    PubMed

    Brown, Judith D; O'Neill, Rachel J

    2010-01-01

    Since Darwin first noted that the process of speciation was indeed the "mystery of mysteries," scientists have tried to develop testable models for the development of reproductive incompatibilities-the first step in the formation of a new species. Early theorists proposed that chromosome rearrangements were implicated in the process of reproductive isolation; however, the chromosomal speciation model has recently been questioned. In addition, recent data from hybrid model systems indicates that simple epistatic interactions, the Dobzhansky-Muller incompatibilities, are more complex. In fact, incompatibilities are quite broad, including interactions among heterochromatin, small RNAs, and distinct, epigenetically defined genomic regions such as the centromere. In this review, we will examine both classical and current models of chromosomal speciation and describe the "evolving" theory of genetic conflict, epigenetics, and chromosomal speciation. PMID:20438362

  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. PMID:11084629

  18. JESS, A joint expert speciation system-I. Raison d'être.

    PubMed

    May, P M; Murray, K

    1991-12-01

    JESS is a new computer package for modelling chemical systems in solution and performing numerical analyses on associated experimental data. It was developed to solve problems requiring specialist knowledge of chemical speciation. It currently comprises over 150 programs, 1200 subroutines and 120,000 lines of Fortran code. The main reasons for the development of JESS, and the principles which underpin it, are described. Subsequent papers detail the major facilities which JESS now provides. PMID:18965317

  19. 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

  20. Speciation by Symbiosis: the Microbiome and Behavior.

    PubMed

    Shropshire, J Dylan; Bordenstein, Seth R

    2016-01-01

    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

  1. 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

  2. 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. PMID:22529005

  3. 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.

  4. Complex speciation of humans and chimpanzees.

    PubMed

    Wakeley, John

    2008-03-13

    Genetic data from two or more species provide information about the process of speciation. In their analysis of DNA from humans, chimpanzees, gorillas, orangutans and macaques (HCGOM), Patterson et al. suggest that the apparently short divergence time between humans and chimpanzees on the X chromosome is explained by a massive interspecific hybridization event in the ancestry of these two species. However, Patterson et al. do not statistically test their own null model of simple speciation before concluding that speciation was complex, and--even if the null model could be rejected--they do not consider other explanations of a short divergence time on the X chromosome. These include natural selection on the X chromosome in the common ancestor of humans and chimpanzees, changes in the ratio of male-to-female mutation rates over time, and less extreme versions of divergence with gene flow (see ref. 2, for example). I therefore believe that their claim of hybridization is unwarranted. PMID:18337768

  5. Monte Carlo simulations of parapatric speciation

    NASA Astrophysics Data System (ADS)

    Schwämmle, V.; Sousa, A. O.; de Oliveira, S. M.

    2006-06-01

    Parapatric speciation is studied using an individual-based model with sexual reproduction. We combine the theory of mutation accumulation for biological ageing with an environmental selection pressure that varies according to the individuals geographical positions and phenotypic traits. Fluctuations and genetic diversity of large populations are crucial ingredients to model the features of evolutionary branching and are intrinsic properties of the model. Its implementation on a spatial lattice gives interesting insights into the population dynamics of speciation on a geographical landscape and the disruptive selection that leads to the divergence of phenotypes. Our results suggest that assortative mating is not an obligatory ingredient to obtain speciation in large populations at low gene flow.

  6. 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...

  7. 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...

  8. 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.

  9. Thermal enrichment and speciation of copper in rice husk ashes.

    PubMed

    Wei, Yu-Ling; Hu, Ming-Jan; Peng, Yen-Hsun

    2010-12-15

    Copper(II) was considerably enriched in the residual ash via thermal treatment of copper-sorbed rice husk at 700-1100°C for 2h, and the copper speciation was quantitatively determined with X-ray absorption spectroscopy. After the thermal process, the resulting ash only represents by weight 18.7-26.4% of the pre-heated samples. Copper content in the ashes is >7% which is far above the required minimum copper content in copper ores for the copper smelting sector, 0.5%. Crystalline SiO(2) is observed only in the ash generated at 1100°C, with more copper in this ash being available for leaching in acidic solution. It is suggested that this is due to the considerable dissimilarity in crystalline structure between copper compounds and crystalline SiO(2). No chemical reaction between copper and SiO(2) is observed in any ash. In fact, we suggest that the SiO(2) crystalline phase repels copper during the thermal process; this would make it easy to extract copper from the ashes. For copper speciation in the ashes, CuO merely represents 0-12% of the total copper, while Cu(2)O and Cu(0) represent 34-42% and 46-63%, respectively. The lower copper oxidation state would be beneficial for the copper smelting process due to less usage of coke. PMID:20869164

  10. 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

  11. 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

  12. 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. PMID:9766084

  13. 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.

  14. 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.

  15. Sample treatment in chromatography-based speciation of organometallic pollutants.

    PubMed

    Gómez-Riza, J L; Morales, E; Giráldez, I; Sánchez-Rodas, D; Velasco, A

    2001-12-14

    Speciation analysis is nowadays performed routinely in many laboratories to control the quality of the environment, food and health. Chemical speciation analyses generally include the study of different oxidation state of elements or individual organometallic compounds. The determination of the different chemical forms of elements is still an analytical challenge, since they are often unstable and concentrations in different matrices of interest are in the microg l(-1) or even in the ng l(-1) range (e.g., estuarine waters) or ng g(-1) in sediments and biological tissues. For this reason, sensitive and selective analytical atomic techniques are being used as available detectors for speciation, generally coupled with chromatography for the time-resolved introduction of analytes into the atomic spectrometer. The complexity of these instrumental couplings has a straightforward consequence on the duration of the analysis, but sample preparation to separate and transfer the chemical species present in the sample into a solution to be accepted readily by a chromatographic column is the more critical step of total analysis, and demands considerable operator skills and time cost. Traditionally, liquid-liquid extraction has been employed for sample treatment with serious disadvantages, such as consumption, disposal and long-term exposure to organic solvent. In addition, they are usually cumbersome and time-consuming. Therefore, the introduction of new reagents such as sodium tetraethylborate for the simultaneous derivatization of several elements has been proposed. Other possibilities are based in the implementation of techniques for efficient and accelerated isolation of species from the sample matrix. This is the case for microwave-assisted extraction, solid-phase extraction and microextraction, supercritical fluid extraction or pressurized liquid extraction, which offer new possibilities in species treatment, and the advantages of a drastic reduction of the extraction

  16. 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

  17. Ecological speciation in tropical reef fishes

    PubMed Central

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

    2005-01-01

    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. PMID:15817431

  18. NICKEL SPECIATION OF RESIDUAL OIL ASH

    EPA Science Inventory

    EPA GRANT NUMBER: R827649C002
    Title: Nickel Speciation Of Residual Oil Ash
    Investigators: Kevin C. Galbreath, John Won, Frank E. Huggins, Gerald P. Huffman, Christopher J. Zygarlicke, Donald L. Toman
    Institution: University of North Dakota<...

  19. 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

  20. 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.

  1. 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

  2. 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...

  3. 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.

  4. Heavy metal speciation in the composting process.

    PubMed

    Greenway, Gillian M; Song, Qi Jun

    2002-04-01

    Composting is one of the more efficient and environment friendly methods of solid waste disposal and has many advantages when compared with landfill disposal on which the UK and Ireland are currently heavily dependent. Composting is a very complicated process involving intensive microbial activity and the detailed mechanisms of the process have yet to be fully understood. Metal speciation information can provide an insight into the metal-microbial interaction and would help in the evaluation of the quality of compost. This would facilitate the exploitation of composts in remediation of heavy metal contaminated land. In this work a systematic approach to metal speciation in compost has been taken by applying the three-step method for operationally defined metal speciation of soils and sediments, developed by the European Commission's Standards, Measurement and Testing Programme to monitor the change in metal speciation with time (up to 106 days) for four different waste composting processes. The results have shown that in general metals become less available for the first extraction step as the composting process proceeds. This implies that composting tends to redistribute the metals from more labile forms to more fixed forms which may explain why the application of composts could be useful for with heavy metal contaminated land. There are exceptions to this trend and in some cases, certain metals appear to behave differently depending on the source of the compost. PMID:11993774

  5. 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...

  6. 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 ...

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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).

  12. 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.

  13. The speciation of marine particulate iron adjacent to active and passive continental margins

    NASA Astrophysics Data System (ADS)

    Lam, Phoebe J.; Ohnemus, Daniel C.; Marcus, Matthew A.

    2012-03-01

    We use synchrotron-based chemical-species mapping techniques to compare the speciation of suspended (1-51 μm) marine particulate iron collected in two open ocean environments adjacent to active and passive continental margins. Chemical-species mapping provides speciation information for heterogeneous environmental samples, and is especially good for detecting spectroscopically distinct trace minerals and species that could not be detectable by other methods. The average oxidation state of marine particulate iron determined by chemical-species mapping is comparable to that determined by standard bulk X-ray Absorption Near Edge Structure spectroscopy. Using chemical-species mapping, we find that up to 43% of particulate Fe in the Northwest Pacific at the depth of the adjacent active continental margin is in the Fe(II) state, with the balance Fe(III). In contrast, particulate iron in the eastern tropical North Atlantic, which receives the highest dust deposition on Earth and is adjacent to a passive margin, is dominated by weathered and oxidized Fe compounds, with Fe(III) contributing 90% of total iron. The balance is composed primarily of Fe(II)-containing species, but we detected individual pyrite particles in some samples within an oxygen minimum zone in the upper thermocline. Several lines of evidence point to the adjacent Mauritanian continental shelf as the source of pyrite to the water column. The speciation of suspended marine particulate iron reflects the mineralogy of iron from the adjacent continental margins. Since the solubility of particulate iron has been shown to be a function of its speciation, this may have implications for the bioavailability of particulate iron adjacent to passive compared to active continental margins.

  14. 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...

  15. Speciation and release kinetics of cadmium in an alkaline paddy soil under various flooding periods and draining conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Understanding the chemical forms in which Cd is present in paddy soils is needed to develop efficient and cost-effective strategies to clean up the soils, and/or minimize Cd uptake by rice. This study aims to determine Cd speciation and release kinetics in an alkaline paddy soil, at various flooding...

  16. 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.

  17. 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.

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

    USGS Publications Warehouse

    Kim, C.S.; Brown, Gordon E., Jr.; 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

  19. 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

  20. 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

  1. 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.

  2. 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

  3. Chiral Speciation in Terrestrial Pulmonate Snails

    PubMed Central

    Gittenberger, Edmund; Hamann, Thomas D.; Asami, Takahiro

    2012-01-01

    On the basis of data in the literature, the percentages of dextral versus sinistral species of snails have been calculated for western Europe, Turkey, North America (north of Mexico), and Japan. When the family of Clausiliidae is represented, about a quarter of all snail species may be sinistral, whereas less than one per cent of the species may be sinistral where that family does not occur. The number of single-gene speciation events on the basis of chirality, resulting in the origin of mirror image species, is not closely linked to the percentage of sinistral versus dextral species in a particular region. Turkey is nevertheless exceptional by both a high percentage of sinistral species and a high number of speciation events resulting in mirror image species. Shell morphology and genetic background may influence the ease of chirality-linked speciation, whereas sinistrality may additionally be selected against by internal selection. For the Clausiliidae, the fossil record and the recent fauna suggest that successful reversals in coiling direction occurred with a frequency of once every three to four million years. PMID:22532825

  4. Non-chromatographic atomic spectrometric methods in speciation analysis: A review

    NASA Astrophysics Data System (ADS)

    Vieira, Mariana A.; Grinberg, Patricia; Bobeda, Cláudio R. R.; Reyes, Mariela N. M.; Campos, Reinaldo C.

    2009-06-01

    In recent years, knowledge of the different chemical forms of the elements has gained increasing importance. There has been significant progress in methods that hyphenate chromatographic separations with atomic spectrometry. These hyphenated methods can provide the most complete information on the species distribution and even structure. However, they can be lengthy, relatively costly and difficult to bring to the routine. On the other hand, it is important to remember that chromatographic techniques represent only a minor part of the separation procedures available and, in certain cases, the application of basic chemistry to sample treatments can give quantitative information about specific chemical forms. In this sense, non-chromatographic procedures can provide methods that offer sufficient information on the elemental speciation for a series of situations. Moreover, these non-chromatographic strategies can be less time consuming, more cost effective and available, and present competitive limits of detection. Thus, non-chromatographic speciation analysis continues to be a promising research area and has been applied to the development of several methodologies that facilitate this type of analytical approach. In view of their importance, the present work overviews and discusses different non-chromatographic methods as alternatives for the speciation analysis of clinical, environmental and food samples using atomic spectrometry for detection.

  5. 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.

  6. 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.

  7. 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. PMID:12600761

  8. 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.

  9. 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

  10. 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

  11. 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

  12. 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

  13. 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

  14. Phosphorus Speciation in Skeletal Aragonite of Deep Sea Corals

    NASA Astrophysics Data System (ADS)

    Mason, H. E.; Montagna, P.; Phillips, B. L.

    2007-12-01

    Phosphorus plays an important role in the world oceans as a limiting nutrient and can serve as an indicator of productivity. This link to bioactivity also relates P concentration to changes in atmospheric CO2 through biotic sequestration. The P concentration of ocean water is also connected to changes in deep sea ocean circulation that are also vehicles for global climate change. A paleoproxy for oceanic P concentration recently has been developed based on the P content in skeletal aragonite of deep-sea corals. The P-content of the septa record the ambient ocean P concentration at the time the time of deposition, which can be measured at high spatial resolution by methods such as ICP-MS. Although the correlation of P content of coral aragonite and ambient seawater suggests that phosphate is incorporated into the aragonite structure during crystal growth, the P speciation in the skeletal aragonite is unknown. We have studied P speciation in deep-sea coral aragonite collected from various localities using P-31 single pulse (SP) and cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopic techniques. Spectra of all samples contain a broad peak (>6 ppm full width at half maximum; FWHM) at a chemical shift of 3.0 to 3.5 ppm which is tentatively assigned to phosphate defects in the aragonite structure. Variable contact time CP/MAS NMR spectra indicates that the broad peak at 3.0 to 3.5 ppm is enhanced at short CP contact times, suggesting that H bearing species are important for accommodating phosphate in the aragonite structure. A subset of the samples gives spectra containing an additional, narrow peak (~ 1.5 ppm FWHM) at a chemical shift of 2.6 ppm. The spectral characteristics of this narrow peak, including both chemical shift and CP dynamics, are similar those of hydroxyl-containing apatite phases. On this basis and the small width of the peak it is assigned to crystalline apatite inclusions. These inclusions account for up to

  15. PHREEQC. Geochemical Speciation Mass Transfer

    SciTech Connect

    Parkhurst, D.L.

    1995-01-01

    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 mineral 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.

  16. 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.

  17. Case studies and mathematical models of ecological speciation. 4. Hybrid speciation in butterflies in a jungle.

    PubMed

    Duenez-Guzman, Edgar A; Mavárez, Jesus; Vose, Michael D; Gavrilets, Sergey

    2009-10-01

    We build a spatial individual-based multilocus model of homoploid hybrid speciation tailored for a tentative case of hybrid origin of Heliconius heurippa from H. melpomene and H. cydno in South America. Our model attempts to account for empirical patterns and data on genetic incompatibility, mating preferences and selection by predation (both based on coloration patterns), habitat preference, and local adaptation for all three Heliconius species. Using this model, we study the likelihood of recombinational speciation and identify the effects of various ecological and genetic parameters on the dynamics, patterns, and consequences of hybrid ecological speciation. Overall, our model supports the possibility of hybrid origin of H. heurippa under certain conditions. The most plausible scenario would include hybridization between H. melpomene and H. cydno in an area geographically isolated from the rest of both parental species with subsequent long-lasting geographic isolation of the new hybrid species, followed by changes in the species ranges, the secondary contact, and disappearance of H. melpomene-type ecomorph in the hybrid species. However, much more work (both empirical and theoretical) is necessary to be able to make more definite conclusions on the importance of homoploid hybrid speciation in animals. PMID:19545268

  18. 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

  19. 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

  20. Speciation and release kinetics of zinc in contaminated paddy soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Zinc is an important nutrient for plants, but it can be toxic at high concentrations. The solubility and speciation of Zn is controlled by many factors, especially soil pH and Eh, which can vary in lowland rice culture. This study determined Zn speciation and release kinetics in Cd-Zn co-contamina...

  1. Passenger car hydrocarbon emissions speciation. Final report

    SciTech Connect

    Black, F.; High, L.

    1980-05-01

    Emission factors for over 60 individual hydrocarbon compounds were determined for four passenger cars. The cars included a 1963 Chevrolet, a 1977 Mustang, and 1978 Monarch, and 1979 LTD II. The speciation data is reported for both tailpipe and evaporative emissions. The tailpipe emissions were for the urban driving conditions of the Federal Test Procedure used in motor vehicle certification. The evaporative emissions were for both diurnal and hot soak conditions, also prescribed in the Federal Test Procedure for certification. The vehicle tests involved four gasoline fuels of varying composition.

  2. 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.

  3. 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

  4. Linking emergence of fungal plant diseases and ecological speciation

    PubMed Central

    Giraud, Tatiana; Gladieux, Pierre; Gavrilets, Sergey

    2010-01-01

    Emerging diseases represent a growing worldwide problem accompanying global environmental changes, and there is tremendous interest in identifying the factors controlling the appearance and spread of these diseases. Here, we discuss emerging fungal plant diseases, and argue that they often result from host shift speciation, a particular case of ecological speciation. We consider the factors controlling local adaptation and ecological speciation and show that certain life-history traits of many fungal plant pathogens are conducive for rapid ecological speciation, thus favoring the emergence of novel pathogen species adapted to new hosts. We argue that placing the problem of emerging fungal diseases of plants within the context of ecological speciation can significantly improve our understanding of the biological mechanisms governing emergence of such diseases. PMID:20434790

  5. Sympatric speciation as a consequence of male pregnancy in seahorses

    PubMed Central

    Jones, Adam G.; Moore, Glenn I.; Kvarnemo, Charlotta; Walker, DeEtte; Avise, John C.

    2003-01-01

    The phenomenon of male pregnancy in the family Syngnathidae (seahorses, pipefishes, and sea dragons) undeniably has sculpted the course of behavioral evolution in these fishes. Here we explore another potentially important but previously unrecognized consequence of male pregnancy: a predisposition for sympatric speciation. We present microsatellite data on genetic parentage that show that seahorses mate size-assortatively in nature. We then develop a quantitative genetic model based on these empirical findings to demonstrate that sympatric speciation indeed can occur under this mating regime in response to weak disruptive selection on body size. We also evaluate phylogenetic evidence bearing on sympatric speciation by asking whether tiny seahorse species are sister taxa to large sympatric relatives. Overall, our results indicate that sympatric speciation is a plausible mechanism for the diversification of seahorses, and that assortative mating (in this case as a result of male parental care) may warrant broader attention in the speciation process for some other taxonomic groups as well. PMID:12732712

  6. Metal speciation dynamics in monodisperse soft colloidal ligand suspensions.

    PubMed

    Duval, Jérôme F L; Pinheiro, José P; van Leeuwen, Herman P

    2008-08-01

    A comprehensive theory is presented for the dynamics of metal speciation in monodisperse suspensions of soft spherical particles characterized by a hard core and an ion-permeable shell layer where ligands L are localized. The heterogeneity in the binding site distribution leads to complex formation/dissociation rate constants (denoted as k a (*) and k d (*), respectively) that may substantially differ from their homogeneous solution counterparts (k a and k d). The peculiarities of metal speciation dynamics in soft colloidal ligand dispersions result from the coupling between diffusive transport of free-metal ions M within and around the soft surface layer and the kinetics of ML complex formation/dissociation within the shell component of the particle. The relationship between k a,d (*) and k a,d is derived from the numerical evaluation of the spatial, time-dependent distributions of free and bound metal. For that purpose, the corresponding diffusion equations corrected by the appropriate chemical source term are solved in spherical geometry using a Kuwabara-cell-type representation where the intercellular distance is determined by the volume fraction of soft particles. The numerical study is supported by analytical approaches valid in the short time domain. For dilute dispersions of soft ligand particles, it is shown that the balance between free-metal diffusion within and outside of the shell and the kinetic conversion of M into ML within the particular soft surface layer rapidly establishes a quasi-steady-state regime. For sufficiently long time, chemical equilibrium between the free and bound metal is reached within the reactive particle layer, which corresponds to the true steady-state regime for the system investigated. The analysis reported covers the limiting cases of rigid particles where binding sites are located at the very surface of the particle core (e.g., functionalized latex colloids) and polymeric particles that are devoid of a hard core (e

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. Global patterns of speciation and diversity.

    PubMed

    de Aguiar, M A M; Baranger, M; Baptestini, E M; Kaufman, L; Bar-Yam, Y

    2009-07-16

    In recent years, strikingly consistent patterns of biodiversity have been identified over space, time, organism type and geographical region. A neutral theory (assuming no environmental selection or organismal interactions) has been shown to predict many patterns of ecological biodiversity. This theory is based on a mechanism by which new species arise similarly to point mutations in a population without sexual reproduction. Here we report the simulation of populations with sexual reproduction, mutation and dispersal. We found simulated time dependence of speciation rates, species-area relationships and species abundance distributions consistent with the behaviours found in nature. From our results, we predict steady speciation rates, more species in one-dimensional environments than two-dimensional environments, three scaling regimes of species-area relationships and lognormal distributions of species abundance with an excess of rare species and a tail that may be approximated by Fisher's logarithmic series. These are consistent with dependences reported for, among others, global birds and flowering plants, marine invertebrate fossils, ray-finned fishes, British birds and moths, North American songbirds, mammal fossils from Kansas and Panamanian shrubs. Quantitative comparisons of specific cases are remarkably successful. Our biodiversity results provide additional evidence that species diversity arises without specific physical barriers. This is similar to heavy traffic flows, where traffic jams can form even without accidents or barriers. PMID:19606148

  12. Gene regulation and speciation in house mice.

    PubMed

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

    2016-04-01

    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 betweenMus musculus musculusandM. m. domesticuswas characterized by studying allele-specific expression in fertile hybrid males using mRNA-sequencing of whole testes. We found extensive regulatory divergence betweenM. m. musculusandM. m. domesticus, largely attributable tocis-regulatory changes. When bothcisandtranschanges 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

  13. 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

  14. 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

  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. 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. PMID:26633236

  17. 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.

  18. 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...

  19. 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...

  20. 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...

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Genome-wide congealing and rapid transitions across the speciation continuum during speciation with gene flow.

    PubMed

    Feder, Jeffrey L; Nosil, Patrik; Wacholder, Aaron C; Egan, Scott P; Berlocher, Stewart H; Flaxman, Samuel M

    2014-01-01

    Our current understanding of speciation is often based on considering a relatively small number of genes, sometimes in isolation of one another. Here, we describe a possible emergent genome process involving the aggregate effect of many genes contributing to the evolution of reproductive isolation across the speciation continuum. When a threshold number of divergently selected mutations of modest to low fitness effects accumulate between populations diverging with gene flow, nonlinear transitions can occur in which levels of adaptive differentiation, linkage disequilibrium, and reproductive isolation dramatically increase. In effect, the genomes of the populations start to "congeal" into distinct entities representing different species. At this stage, reproductive isolation changes from being a characteristic of specific, divergently selected genes to a property of the genome. We examine conditions conducive to such genome-wide congealing (GWC), describe how to empirically test for GWC, and highlight a putative empirical example involving Rhagoletis fruit flies. We conclude with cautious optimism that the models and concepts discussed here, once extended to large numbers of neutral markers, may provide a framework for integrating information from genome scans, selection experiments, quantitative trait loci mapping, association studies, and natural history to develop a deeper understanding of the genomics of speciation. PMID:25149256

  7. 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.

  8. 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

  9. 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

  10. Speciation of arsenic in sulfidic waters

    PubMed Central

    Wilkin, Richard T; Wallschläger, Dirk; Ford, Robert G

    2003-01-01

    Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH2S from 10-7.5 to 10-3.0 M, ΣAs from 10-5.6 to 10-4.8 M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH)30, and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10-4.3 M at neutral pH. Conversion from neutral As(OH)30 to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions.

  11. 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

  12. 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

  13. 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

  14. Nitrogen speciation in mantle and crustal fluids

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Keppler, Hans

    2014-03-01

    Seventy-nine experiments have been carried out at 600-1400 °C, 2-35 kbar, and oxygen fugacities ranging from the Fe-FeO to the Re-ReO2 buffer to investigate the nitrogen speciation in mantle and crustal N-H-O fluids. Laser Raman analyses of fluid inclusions trapped in situ in quartz and olivine crystals show that N2 and/or NH3 are the only detectable nitrogen species in the fluids at the conditions of the present study. The results further show that in the fluids of the oxidized shallow upper mantle, nitrogen is mostly present as N2, while in the deep reduced upper mantle, NH3 is the dominant nitrogen species. Nitrogen speciation in subduction zone fluids is also calculated from the experimental data to constrain the efficiency of nitrogen recycling. The data show that a hot, oxidized slab is an efficient barrier for deep nitrogen subduction, while a cold, reduced slab would favor recycling nitrogen into the deep mantle. The nitrogen species in magmatic fluids of mid-ocean ridge basalt and arc magmas are predominantly N2, but a significant fraction of nitrogen can be NH3 at certain conditions. The nitrogen species in fluids released from the solidifying magma ocean and the reduced young mantle may have been mostly NH3. The release of such fluids may have created a reduced atmosphere on the every early Earth, with an elevated concentration of NH3. This may not only resolve the faint young Sun paradox but may also have created favorable conditions for the formation of biomolecules through Miller-Urey type reactions.

  15. 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

  16. Polyploidy in relation to plant evolution and speciation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polyploidy is a dominant force in plant evolution and speciation. Allopolyploids, resulting from interspecific or intergeneric hybridization coupled with chromosome doubling, are preponderant in nature. For the meiotic and reproductive stability of the allopolyploids, a precise genetic control of ...

  17. ACTINIDE-ALUMINATE SPECIATION IN ALKALINE RADIOACTIVE WASTE

    EPA Science Inventory

    Highly alkaline radioactive waste tanks contain a number of transuranic species, in particular U, Np, Pu, and Am - the exact forms of which are currently unknown. Knowledge of actinide speciation under highly alkaline conditions is essential towards understanding and predicting ...

  18. 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. PMID:26612568

  19. 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) ...

  20. 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

  1. 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. PMID:26814593

  2. 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

  3. Ecological Impacts of Reverse Speciation in Threespine Stickleback.

    PubMed

    Rudman, Seth M; Schluter, Dolph

    2016-02-22

    Young species are highly prone to extinction via increased gene flow after human-caused environmental changes. This mechanism of biodiversity loss, often termed reverse speciation or introgressive extinction, is of exceptional interest because the parent species are typically highly differentiated ecologically. Reverse speciation events are potentially powerful case studies for the role of evolution in driving ecological changes, as the phenotypic shifts associated with introgressive extinction can be large and they occur over particularly short timescales. Furthermore, reverse speciation can lead to novel phenotypes, which may in turn produce novel ecological effects. Here we investigate the ecological shift associated with reverse speciation in threespine stickleback fish using a field study and a replicated experiment. We find that an instance of introgressive extinction had cascading ecological consequences that altered the abundance of both aquatic prey and the pupating aquatic insects that emerged into the terrestrial ecosystem. The community and ecosystem impacts of reverse speciation were novel, and yet they were also predictable based on ecological and morphological considerations. The study suggests that knowledge about the community ecology and changes in functional morphology of a dominant species may lead to some predictive power for the ecological effects of evolutionary change. Moreover, the rapid nature and resultant ecological impacts associated with reverse speciation demonstrates the interplay between biodiversity, evolutionary change, and ecosystem function. PMID:26804556

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. Assessment of occupational exposure to inorganic arsenic based on urinary concentrations and speciation of arsenic.

    PubMed

    Farmer, J G; Johnson, L R

    1990-05-01

    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

  11. 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

  12. Iodine speciation in rain, snow and aerosols

    NASA Astrophysics Data System (ADS)

    Gilfedder, B. S.; Lai, S. C.; Petri, M.; Biester, H.; Hoffmann, T.

    2008-10-01

    Iodine oxides, such as iodate, should be the only thermodynamically stable sink species for iodine in the troposphere. However, field observations have increasingly found very little iodate and significant amounts of iodide and soluble organically bound iodine (SOI) in precipitation and aerosols. The aim of this study was to investigate iodine speciation, including the organic fraction, in rain, snow, and aerosols in an attempt to further clarify aqueous phase iodine chemistry. Diurnal aerosol samples were taken with a 5 stage cascade impactor and a virtual impactor (PM2.5) from the Mace Head research station, Ireland, during summer 2006. Rain was collected from Australia, New Zealand, Patagonia, Germany, Ireland, and Switzerland and snow was obtained from Greenland, Germany, Switzerland, and New Zealand. Aerosols were extracted from the filters with water and all samples were analysed for total soluble iodine (TSI) by inductively coupled plasma mass spectrometry (ICP-MS) and iodine speciation was determined by coupling an ion chromatography unit to the ICP-MS. The median concentration of TSI in aerosols from Mace Head was 222 pmol m-3 (summed over all impactor stages) of which the majority was associated with the SOI fraction (median day: 90±4%, night: 94±2% of total iodine). Iodide exhibited higher concentrations than iodate (median 6% vs. 1.2% of total iodine), and displayed significant enrichment during the day compared to the night. Interestingly, up to 5 additional, presumably anionic iodo-organic peaks were observed in all IC-ICP-MS chromatograms, composing up to 15% of the TSI. Soluble organically bound iodine was also the dominant fraction in all rain and snow samples, with lesser amounts of iodide and iodate (iodate was particularly low in snow). Two of the same unidentified peaks found in aerosols were also observed in precipitation from both Southern and Northern Hemispheres. This suggests that these species are transferred from the aerosols into

  13. Testing copper-speciation predictions in freshwaters over a wide range of metal-organic matter ratios.

    PubMed

    Ahmed, Imad A M; Hamilton Taylor, John; Lofts, Stephen; Meeussen, Johannes C L; Lin, Chun; Zhang, Hao; Davison, William

    2013-02-01

    The harsh chemical conditions involved in the isolation of fulvic acids (FA) and humic acids (HA) have been identified as a possible contributing factor to the significant mismatch between in situ measurements and model predictions of trace metal speciation in freshwaters, resulting from the use of isolated FA and HA in model calibration. A set of experimental assays were developed to enable Cu binding to DOM to be measured over the full range of [Cu]/[DOC] ratios (∼1-460 μmol g(-1)) observed in surface freshwaters. They were applied to the widely used and traditionally isolated Suwannee River HA and FA and to DOM isolated from headwater streams by a mild procedure using minimal chemical treatment. Good agreement was observed between measured free ion activities and those predicted using both WHAM/Model VII and NICA-Donnan speciation models for both traditionally and mildly isolated DOM. Agreement to within a factor of 2 for WHAM/Model VII contrasts with 100-fold differences previously reported between in situ Cu(2+) measurements and model predictions for a wide range of conditions. The results demonstrate that (a) existing speciation models are capable of accurately predicting Cu-humic binding in natural waters at environmentally realistic [Cu]/[DOC] ratios, under equilibrium conditions, and (b) that the isolation procedures traditionally used for HA and FA do not appreciably affect their binding characteristics. PMID:23286231

  14. 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

  15. 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. PMID:21476358

  16. 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

  17. 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.

  18. Arsenic and chromium speciation in an urban contaminated soil.

    PubMed

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

    2012-08-01

    The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)⋅2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil. PMID:22520924

  19. Phosphorous speciation in surface sediments of the Cochin estuary.

    PubMed

    Gireeshkumar, T R; Deepulal, P M; Chandramohanakumar, N

    2013-03-01

    Sequential chemical extraction using chelating agents were used to study the P dynamics and its bioavailability along the surface sediments of the Cochin estuary (southwest coast of India). Sediments were analyzed for major P species (iron bound P, calcium bound P, acid soluble organic P, alkali soluble organic P and residual organic P), Fe, Ca, total carbon, organic carbon, total nitrogen and total sulfur contents. An abrupt increase in the concentration of dissolved inorganic P with increasing salinity was observed in the study region. Iron-bound P exhibited a distinct seasonal pattern with maximum values in the monsoon season when fresh water condition was prevailed in the estuary. As salinity increased, the percentage of iron-bound P decreased, while that of calcium-bound P and total sedimentary sulfur increased. C/P and N/P ratios were low which indicate that large amounts of organic matter enriched with P tend to accumulate in surface sediments. The high organic P contribution in the sedimentary P pool may indicate high organic matter load with incomplete mineralization, as well as comparatively greater percentage of humic substance and resistant organic compounds. Principal component analysis is employed to find the possible processes influencing the speciation of P in the study region and indicate the following processes: (1) the spatial and seasonal variations of calcium bound P and acid soluble organic P was mainly controlled by sediment texture and organic carbon content, (2) sediment redox conditions control the distribution of iron bound P and (3) the terrigenous input of organic P is a significant processes controlling total P content in surface sediments. The bioavailable P was very high in the surface sediments which on an average accounts for 59 % in the pre-monsoon, 65 % in the monsoon and 53 % in the post-monsoon seasons. The surface sediments act as a potential internal source of P in the Cochin estuary. PMID:22843296

  20. 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

  1. Clinical applications of HPLC-ICP-MS element speciation: A review.

    PubMed

    Delafiori, Jeany; Ring, Gavin; Furey, Ambrose

    2016-06-01

    Arsenic (As), Selenium (Se) and Mercury (Hg) are three trace elements that have been the subject of much analytical discussion and investigation over the last three decades. While Selenium (Se) is among the list of essential trace elements necessary for the regulation of metabolic processes and overall health, As and Hg are not, and have been the centre of various cases surrounding the contamination of food, water and the environment. The focus of this review is to explore the area of chemical speciation, particularly as it relates to the measurement of these elements in various clinical matrices by HPLC-ICP-MS. This review will highlight the importance of accurately identifying the various chemical species of each of these elements, especially when considering their respective toxicological impacts on human health. PMID:27130123

  2. XANES spectroscopic analysis of phosphorus speciation in alum-amended poultry litter.

    PubMed

    Seiter, Jennifer M; Staats-Borda, Kristin E; Ginder-Vogel, Matthew; Sparks, Donald L

    2008-01-01

    Aluminum sulfate (alum; Al(2)(SO(4))(3).14H(2)O) 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 ( approximately 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. PMID:18268311

  3. 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.

  4. Localization and speciation of mercury in brown rice with implications for pan-Asian public health.

    PubMed

    Meng, Bo; Feng, Xinbin; Qiu, Guangle; Anderson, Christopher W N; Wang, Jianxu; Zhao, Lei

    2014-07-15

    Cultivation of paddy rice for human consumption is a dominant agricultural activity throughout Asia. High levels of mercury (Hg) in rice grain pose a potential threat to human health, although the extent of risk is dependent on the chemical speciation of Hg inside the grain. We have investigated the speciation and localization of Hg in three fractions of rice grain (hull, bran, and white rice) collected from a Hg-contaminated region in China. On a mass basis, the majority of inorganic mercury (IHg) in a rice grain is found in hull and bran. However, the majority of the more toxic species methyl mercury (MeHg) is found in edible white rice. Our data show that during grain processing, most of the IHg (∼78%) is eliminated, but the majority of the MeHg remains in the food product (∼80%). Synchrotron radiation microscopic X-ray fluorescence (SR-μXRF) mapping shows strong localization of Hg at the surface of brown rice grains, corresponding to the pericarp and aleurone layer. We infer that this Hg is predominantly IHg absorbed from the atmosphere. Based on X-ray absorption near-edge spectroscopy (XANES) data we propose that IHg in bran is primarily bound to cysteine, and is associated with phytochelatins. Consequently, IHg is largely immobile and restricted to the outer layers of rice grain. MeHg in bran is primarily bound to cysteine and is associated with proteins. However, this MeHg-cysteine association behaves like a mobile nutrient and is actively transported to the endosperm during seed ripening. Concentration of MeHg-cysteine in white rice has implications for public health. There is growing evidence for Hg contamination of rice throughout Asia due to point and diffuse sources of Hg pollution. The magnitude of the associated risk must be quantified through better understanding of the localization and speciation of mercury in rice. Our work makes an effort to contribute to this understanding. PMID:24925231

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. Mercury speciation on three European mining districts by XANES techniques

    NASA Astrophysics Data System (ADS)

    Esbri, J. M.; Garcia-Noguero, E. M.; Guerrero, B.; Kocman, D.; Bernaus, A.; Gaona, X.; Higueras, P.; Alvarez, R.; Loredo, J.; Horvat, M.; Ávila, M.

    2009-04-01

    The mobility, bioavailability and toxicity of mercury in the environment depend on the chemical species in which is present in soil, sediments, water or air. In this work we used synchrotron radiation to determine mercury species in geological samples of three mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). The aim of this study was to find differences on mobility and bioavailability of mercury on three mining districts with different type of mineralization. For this porpoises we selected samples of ore, calcines, soils and stream sediments from the three sites, completely characterized by the Almadén School of Mines, Josef Stefan Institute of Ljubljana and Oviedo School of Mines. Speciation of mercury was carried out on Synchrotron Laboratories of Hamburg (HASYLAB) by XANES techniques. Spectra of pure compounds [HgCl2, HgSO4, HgO, CH3HgCl, Hg2Cl2 (calomel), HgSred (cinnabar), HgSblack (metacinnabar), Hg2NCl0.5(SO4)0.3(MoO4)0.1(CO3)0.1(H2O) (mosesite), Hg3S2Cl2 (corderoite), Hg3(SO4)O2 (schuetteite) y Hg2ClO (terlinguaite)] were obtained on transmittance mode. The number and type of the compounds required to reconstruct experimental spectra for each sample was obtained by PCA analysis and linear fitting of minimum quadratics of the pure compounds spectra. This offers a semiquantitative approach to the mineralogical constitution of each analyzed sample. The results put forward differences on the efficiency of roasting furnaces from the three studied sites, evidenced by the presence of metacinnabar on the less efficient (Almadén and Asturias) and absence on the most efficient (Idria). For the three studied sites, sulfide species (cinnabar and metacinnabar) were largely more abundant than soluble species (chlorides and sulfates). On the other hand, recent results on the mobility of both Hg and As on the target sites will be presented. These results correlate with the related chemical species found by XANES techniques.

  19. 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.

  20. 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

  1. The relationship of selenium tolerance and speciation in Lecythidaceae species.

    PubMed

    Németh, Anikó; García Reyes, Juan Francisco; Kosáry, Judit; Dernovics, Mihály

    2013-12-01

    Comparative study of selenium (Se) speciation in hyperaccumulator plants offers an interesting challenge from the analytical point of view. In our study the application of a sophisticated sample clean-up procedure and the combination of elemental and molecular mass spectrometric methods led to the identification of several new selenocompounds. The difference between the Se speciation of the primary accumulator Lecythis minor and the secondary accumulator Bertholletia excelsa confirmed the current opinion that the speciation pattern in hyperaccumulator plants is principally related to the mechanism of accumulation and not to taxonomy. The most abundant new selenocompounds were found to be the derivatives of selenohomocysteine (SeHCy) and selenomethionine (SeMet), including fatty acid metabolism related compounds. A series of SeHCy derived species containing multiple Se atoms (>2) was also detected and their structures were validated by the synthesis of their S-Se analogues. PMID:24136350

  2. 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...

  3. Phytoextraction of cadmium by Ipomoea aquatica (water spinach) in hydroponic solution: effects of cadmium speciation.

    PubMed

    Wang, Kai-Sung; Huang, Lung-Chiu; Lee, Hong-Shen; Chen, Pai-Ye; Chang, Shih-Hsien

    2008-06-01

    Phytoextraction is a promising technique to remediate heavy metals from contaminated wastewater. However, the interactions of multi-contaminants are not fully clear. This study employed cadmium, Triton X-100 (TX-100), and EDTA to investigate their interactions on phytotoxicity and Cd phytoextraction of Ipomoea aquatica (water spinach) in simulated wastewater. The Cd speciation was estimated by a chemical equilibrium model and MINEQL+. Statistic regression was applied to evaluate Cd speciation on Cd uptake in shoots and stems of I. aquatica. Results indicated that the root length was a more sensitive parameter than root weight and shoot weight. Root elongation was affected by Cd in the Cd-EDTA solution and TX-100 in the Cd-TX-100 solution. Both the root length and the root biomass were negatively correlated with the total soluble Cd ions. In contrast, Cd phytoextraction of I. aquatic was correlated with the aqueous Cd ions in the free and complex forms rather than in the chelating form. Additionally, the high Cd bioconcentration factors of I. aquatica (375-2227 l kg(-1) for roots, 45-144 l kg(-1) for shoots) imply that I. aquatica is a potential aquatic plant to remediate Cd-contaminated wastewater. PMID:18471856

  4. Detailed characterization and profiles of crankcase and diesel particulate matter exhaust emissions using speciated organics.

    PubMed

    Zielinska, Barbara; Campbell, David; Lawson, Douglas R; Ireson, Robert G; Weaver, Christopher S; Hesterberg, Thomas W; Larson, Timothy; Davey, Mark; Liu, L J Sally

    2008-08-01

    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 an intentional quantitative tracer 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 microg/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

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

    PubMed

    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

  6. 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

  7. [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

  8. 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

  9. Coupled effects of hydrodynamics and biogeochemistry on Zn mobility and speciation in highly contaminated sediments.

    PubMed

    Xie, Minwei; Jarrett, Brooke A; Da Silva-Cadoux, Cécile; Fetters, Kyle J; Burton, G Allen; Gaillard, Jean-François; Packman, Aaron I

    2015-05-01

    Porewater transport and diagenetic reactions strongly regulate the mobility of metals in sediments. We executed a series of laboratory experiments in Gust chamber mesocosms to study the effects of hydrodynamics and biogeochemical transformations on the mobility and speciation of Zn in contaminated sediments from Lake DePue, IL. X-ray absorption spectroscopy (XAS) indicated that the oxidation of surficial sediments promoted the formation of more mobile Zn species. Bulk chemical measurements of porewater, overlying water, and sediment also suggested that this process liberated aqueous metals to porewater and facilitated Zn efflux to the overlying water. In addition, sediment resuspension events increased the release of aqueous metals to both surficial porewater and the overlying water column. XAS analysis indicated that resuspension increased dissolution of Zn-sequestering mineral phases. These results show that both steady slow porewater transport and rapid episodic resuspension are important to the release of metal from fine-grained, low-permeability contaminated sediments. Thus, information on metals speciation and mobility under time-varying overlying flow conditions is essential to understanding the long-term behavior of metals in contaminated sediments. PMID:25875468

  10. 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

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

    PubMed

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

    2005-09-01

    Mine tailing from the El Teniente-Codelco copper mine situated in VI Region of Chile was analysed in order to evaluate the mobility and speciation of copper in the solid material. Mine tailing was sampled after the rougher flotation circuits, and the copper content was measured to 1150 mg kg (-1) dry matter. This tailing was segmented into fractions of different size intervals: 0-38, 38-45, 45-53, 53-75, 75-106, 106-150, 150-212, and >212 microm, respectively. Copper content determination, sequential chemical extraction, and desorption experiments were carried out for each size interval in order to evaluate the speciation of copper. It was found that the particles of smallest size contained 50-60% weak acid leachable copper, whereas only 32% of the copper found in largest particles could be leached in weak acid. Copper oxides and carbonates were the dominating species in the smaller particles, and the larger particles contained considerable amounts of sulphides. PMID:16054920

  12. 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

  13. Sedimentary records of metal speciation in the Yangtze Estuary: role of hydrological events.

    PubMed

    Feng, Chenghong; Zhao, Shou; Wang, Dongxin; Niu, Junfeng; Shen, Zhenyao

    2014-07-01

    Chemical speciation of Al, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb and Zn in two typical (210)Pb-dated sediment cores (i.e., the CJ03 site and CJ06 site) in the Yangtze Estuary was investigated to reveal their different responses to upstream hydrological events. Cluster analysis and correlation analysis (CA) demonstrated that the CJ03 site, which is located in the main river channel, experienced significant influences from river hydrology. Specifically, metals in liable fractions (exchangeable, carbonate, reducible and organic fractions) were sensitive to water fluxes, while conservative fractions (residual fractions) have higher affinity with sediment inputs. By comparison, the CJ06 site in shoal correlated better with total organic carbon (TOC), and was influenced more by the surrounding cities. Evidently decreased sediment discharge and their fluctuated size composition and varied metal concentrations accorded well with the time when the impoundment of dams and disastrous flood occurred. The transformation of metals in liable speciation into conservative phases reflected the intercepting role of dams. Metals in the reducible and organic fractions were significantly affected by the varied redox conditions caused by hydrological events. PMID:24556540

  14. Speciation of Sb in airborne particulate matter, vehicle brake linings, and brake pad wear residues

    NASA Astrophysics Data System (ADS)

    Varrica, D.; Bardelli, F.; Dongarrà, G.; Tamburo, E.

    2013-01-01

    Insights into the speciation of Sb in samples of brake linings, brake pad wear residues, road dust, and atmospheric particulate matter PM10 and PM2.5 were obtained combining several well established and advanced characterization techniques, such as scanning electron microscopy - energy dispersive spectrometry (SEM-EDS), inductively coupled plasma mass spectrometry (ICP-MS) and synchrotron radiation X-ray absorption spectroscopy (SR-XAS). The advantage of SR-XAS is that samples do not undergo any chemical treatment prior to measurements, thus excluding possible alterations. These analyses revealed that the samples of wheel rims dust, road dust, and atmospheric particulate matter are composed by an admixture of Sb(III) and Sb(V) in different relative abundances. Brake linings turned out to be composed by Sb(III) oxide (Sb2O3) and stibnite (Sb2S3). Stibnite was also detected in some of the particulate matter samples. The obtained data suggest that Sb2S3 during the brake abrasion process is easily decomposed forming more stable compounds such as antimony mixed oxidic forms. Sb redox speciation, in particular and well studied circumstances, may enhance the potential and selectivity of this element as a tracer of motor vehicle emissions in apportioning studies.

  15. 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.

  16. Actinide speciation in glass leach-layers: An EXAFS study

    SciTech Connect

    Biwer, B.M.; Soderholm, L.; Greegor, R.B.; Lytle, F.W.

    1996-12-31

    Uranium L{sub 3} X-ray absorption data were obtained from two borosilicate glasses, which are considered as models for radioactive wasteforms, both before and after leaching. Surface sensitivity to uranium speciation was attained by a novel application of simultaneous fluorescence and electron-yield detection. Changes in speciation are clearly discernible, from U(VI) in the bulk to (UO{sub 2}){sup 2+}-uranyl in the leach layer. The leach-layer uranium concentration variations with leaching times are also determined from the data.

  17. [Speciation and its mechanisms: conceptual background and recent advances].

    PubMed

    Colley, Eduardo; Fischer, Marta Luciane

    2013-10-01

    This paper presents a historical approach on general concepts of speciation and its mechanisms, from the primordial ideas to the most recent theories that seek to elucidate the origin of biodiversity. It is common knowledge that speciation is a controversial and complex issue that encompasses virtually all the lines of research of biology, in addition to geology and paleontology. The main objective of the paper is to clarify the theoretical concepts on the origin of the animal species, in the chronological order in which they became established throughout the whole of the development of evolutionary biology as a science. PMID:24473657

  18. Hybrid speciation and independent evolution in lineages of alpine butterflies.

    PubMed

    Nice, Chris C; Gompert, Zachariah; Fordyce, James A; Forister, Matthew L; Lucas, Lauren K; Buerkle, C Alex

    2013-04-01

    The power of hybridization between species to generate variation and fuel adaptation is poorly understood despite long-standing interest. There is, however, increasing evidence that hybridization often generates biodiversity, including via hybrid speciation. We tested the hypothesis of hybrid speciation in butterflies occupying extreme, high-altitude habitats in four mountain ranges in western North America with an explicit, probabilistic model, and genome-wide DNA sequence data. Using this approach, in concert with ecological experiments and observations and morphological data, we document three lineages of hybrid origin. These lineages have different genome admixture proportions and distinctive trait combinations that suggest unique and independent evolutionary histories. PMID:23550755

  19. Uranium speciation in glass corrosion layers: An XAFS study

    SciTech Connect

    Biwer, B.M.; Soderholm, L.; Greegor, R.B.; Lytle, F.W.

    1997-12-31

    Uranium L{sub 3} X-ray absorption data were obtained from two borosilicate glasses, which are considered as models for radioactive wasteforms, both before and after leaching. Surface sensitivity to uranium speciation was attained by a novel application of simultaneous fluorescence and electron-yield detection. Changes in speciation are clearly discernible, from U(VI) in the bulk to (UO{sub 2}){sup 2+}-uranyl in the corrosion layer. The uranium concentrations within the corrosion layer also show variations with leaching times that can be determined from the data.

  20. 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

  1. Evaluation of chromium speciation and transport characteristics in the Hanford Site 100D and 100H areas

    SciTech Connect

    Thornton, E.C.; Amonette, J.E.; Olivier, J.

    1995-08-01

    Field and laboratory investigations have been conducted to define the fate and transport characteristics of chromium contamination present in the 100D/H Areas of the Hanford Site. This information is relevant to assessing the impact of the release of hexavalent chromium to the Columbia River. Included in this study was the determination of the concentration and aqueous speciation of chromium in the unconfined acquifer and an assessment of potential changes in speciation as groundwater passes through the river/acquifer transition zone and mixes with the Columbia River. The results of this study indicate that chromium present within the Hanford acquifer is predominantly in the oxidized hexavalent state. Chromium is apparently stable in the oxidized form owing to its lack of organic matter within the acquifer. A portion of the chromium is removed as groundwater passes through the transition zone due to reduction and precipitation associated with sediment/water interaction processes. Chemical data collected from seep water samples, however, suggests, that most of the hexavalent chromium ultimately discharges into the Columbia River. Dilution of hexavalent chromium subsequently occurs during the mixing of groundwater and river water, with relatively little change taking place in speciation.

  2. Recent Advances in On-Line Methods Based on Extraction for Speciation Analysis of Chromium in Environmental Matrices.

    PubMed

    Trzonkowska, Laura; Leśniewska, Barbara; Godlewska-Żyłkiewicz, Beata

    2016-07-01

    The biological activity of Cr(III) and Cr(VI) species, their chemical behavior, and toxic effects are dissimilar. The speciation analysis of Cr(III) and Cr(VI) in environmental matrices is then of great importance and much research has been devoted to this area. This review presents recent developments in on-line speciation analysis of chromium in such samples. Flow systems have proved to be excellent tools for automation of sample pretreatment, separation/preconcentration of chromium species, and their detection by various instrumental techniques. Analytical strategies used in chromium speciation analysis discussed in this review are divided into categories based on selective extraction/separation of chromium species on solid sorbents and liquid-liquid extraction of chromium species. The most popular strategy is that based on solid-phase extraction. Therefore, this review shows the potential of novel materials designed and used for selective binding of chromium species. The progress in miniaturization of measurement systems is also presented. PMID:26186521

  3. 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

  4. Direct speciation analysis of arsenic in sub-cellular compartments using micro-X-ray absorption spectroscopy

    SciTech Connect

    Bacquart, Thomas; Deves, Guillaume; Ortega, Richard

    2010-07-15

    Identification of arsenic chemical species at a sub-cellular level is a key to understanding the mechanisms involved in arsenic toxicology and antitumor pharmacology. When performed with a microbeam, X-ray absorption near-edge structure ({mu}-XANES) enables the direct speciation analysis of arsenic in sub-cellular compartments avoiding cell fractionation and other preparation steps that might modify the chemical species. This methodology couples tracking of cellular organelles in a single cell by confocal or epifluorescence microscopy with local analysis of chemical species by {mu}-XANES. Here we report the results obtained with a {mu}-XANES experimental setup based on Kirkpatrick-Baez X-ray focusing optics that maintains high flux of incoming radiation (>10{sup 11} ph/s) at micrometric spatial resolution (1.5x4.0 {mu}m{sup 2}). This original experimental setup enabled the direct speciation analysis of arsenic in sub-cellular organelles with a 10{sup -15} g detection limit. {mu}-XANES shows that inorganic arsenite, As(OH){sub 3}, is the main form of arsenic in the cytosol, nucleus, and mitochondrial network of cultured cancer cells exposed to As{sub 2}O{sub 3}. On the other hand, a predominance of As(III) species is observed in HepG2 cells exposed to As(OH){sub 3} with, in some cases, oxidation to a pentavalent form in nuclear structures of HepG2 cells. The observation of intra-nuclear mixed redox states suggests an inter-individual variability in a cell population that can only be evidenced with direct sub-cellular speciation analysis.

  5. 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. PMID:23282039

  6. 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...

  7. 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

  8. Latitude, elevational climatic zonation and speciation in New World vertebrates.

    PubMed

    Cadena, Carlos Daniel; Kozak, Kenneth H; Gómez, Juan Pablo; Parra, Juan Luis; McCain, Christy M; Bowie, Rauri C K; Carnaval, Ana C; Moritz, Craig; Rahbek, Carsten; Roberts, Trina E; Sanders, Nathan J; Schneider, Christopher J; VanDerWal, Jeremy; Zamudio, Kelly R; Graham, Catherine H

    2012-01-01

    Many biodiversity hotspots are located in montane regions, especially in the tropics. A possible explanation for this pattern is that the narrow thermal tolerances of tropical species and greater climatic stratification of tropical mountains create more opportunities for climate-associated parapatric or allopatric speciation in the tropics relative to the temperate zone. However, it is unclear whether a general relationship exists among latitude, climatic zonation and the ecology of speciation. Recent taxon-specific studies obtained different results regarding the role of climate in speciation in tropical versus temperate areas. Here, we quantify overlap in the climatic distributions of 93 pairs of sister species of mammals, birds, amphibians and reptiles restricted to either the New World tropics or to the Northern temperate zone. We show that elevational ranges of tropical- and temperate-zone species do not differ from one another, yet the temperature range experienced by species in the temperate zone is greater than for those in the tropics. Moreover, tropical sister species tend to exhibit greater similarity in their climatic distributions than temperate sister species. This pattern suggests that evolutionary conservatism in the thermal niches of tropical taxa, coupled with the greater thermal zonation of tropical mountains, may result in increased opportunities for allopatric isolation, speciation and the accumulation of species in tropical montane regions. Our study exemplifies the power of combining phylogenetic and spatial datasets of global climatic variation to explore evolutionary (rather than purely ecological) explanations for the high biodiversity of tropical montane regions. PMID:21632626

  9. 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...

  10. 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...

  11. 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...

  12. 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.

  13. 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...

  14. 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 ...

  15. 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...

  16. 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

  17. 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

  18. A recombination suppressor contributes to ecological speciation in OSTRINIA moths

    PubMed Central

    Wadsworth, C B; Li, X; Dopman, E B

    2015-01-01

    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

  19. 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

  20. 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.

  1. Speciation of volatile organic compounds from poultry production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The air consent agreement between EPA and large animal feeding operations (AFO) is designed to determine at what level compounds are being emitted from these facilities. However, the methodology used for quantifying total non-methane hydrocarbons and speciation of volatile organic compounds (VOC) n...

  2. Screening of rice cultivars for grain arsenic concentration and speciation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recently, there has been growing interest in the concentration and speciation of arsenic in rice grain because of concerns with food quality and interest in minimizing any potential risk from dietary exposure. Our objective was to screen a range of rice varieties from the USDA world collection for ...

  3. ANNUAL REPORT. ACTINIDE-ALUMINATE SPECIATION IN ALKALINE RADIOACTIVE WASTE

    EPA Science Inventory

    Highly alkaline radioactive waste tanks contain a number of transuranic species, in particular U, Np, Pu, and Am-the exact forms of which are currently unknown. Knowledge of actinide speciation under highly alkaline conditions is essential towards understanding and predicting the...

  4. 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...

  5. 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. PMID:25219373

  6. 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

  7. 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

  8. 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.

  9. 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

  10. Utility of EXAFS in characterization and speciation of mercury-bearing mine wastes

    USGS Publications Warehouse

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

    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.

  11. Incipient ring speciation revealed by a migratory divide.

    PubMed

    Irwin, Darren E

    2009-07-01

    Ever since Ernst Mayr (1942) called ring species the 'perfect demonstration of speciation', they have attracted much interest from researchers examining how two species evolve from one. In a ring species, two sympatric and reproductively isolated forms are connected by a long chain of intermediate populations that encircle a geographic barrier. Ring species have the potential to demonstrate that speciation can occur without complete geographic isolation, in contrast to the classic model of allopatric speciation. They also allow researchers to examine the causes of reproductive isolation in the contact zone and to use spatial variation to infer the steps by which speciation occurs. According to the classical definition, a ring species must have (i) gradual variation through a chain of populations connecting two divergent and sympatric forms, and (ii) complete or nearly complete reproductive isolation between the terminal forms. But evolutionary biologists now recognize that the process of speciation might often occur with some periods of geographic contact and hybridization between diverging forms; during these phases, even partial reproductive isolation can limit gene flow and permit further divergence to occur. In this issue Bensch et al. (2009) make an exciting and important contribution by extending the ring species concept to a case in which the divergence is much younger and not yet advanced to full reproductive isolation. Their study of geographic variation in willow warblers (Phylloscopus trochilus; Fig. 1) provides a beautiful example of gradual variation through a ring of populations connecting two forms that are partially reproductively isolated where they meet, possibly due to divergent migratory behaviours of the terminal forms. PMID:19457189

  12. Arsenic speciation in rice paddy soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Arsenic can undergo several chemical and microbial transformations in soil, including oxidation/reduction, methylation/demethylation, and volatilization, which could impact arsenic bioavailability for plant uptake. An experiment was conducted in field plots at Stuttgart, AR to determine whether arse...

  13. SPECIATION OF ARSENIC COMPOUNDS IN WATER SUPPLIES

    EPA Science Inventory

    The objectives of this project were to develop and test analytical methods that would allow the chemical form (i.e. valence state or compound) of arsenic in drinking waters to be determined, and to use the methods to analyze samples of drinking water from sources where adverse he...

  14. Simulation of acid-base condition and copper speciation in the fish gill microenvironment.

    PubMed

    Tao, S; Wen, Y; Long, A; Dawson, R; Cao, J; Xu, F

    2001-05-01

    pH, alkalinity, and mucus content in the fish gill microenvironment of carp (Cyprinus carpio) were measured by exposing fish to copper at various water pH levels using an apparatus which separates inspired and expired water. The relationship between pH levels inside and outside of the gill microenvironment, between pH and alkalinity, and between mucus secretion, pH, and copper exposure concentration were modeled. Copper speciation in the surrounding water and in the fish gill microenvironment was simulated using MINTEQA2 chemical equilibrium calculation software. The results of the modeling for pH, alkalinity, and mucus calculation were then adopted as inputs for purposes of parameter identification in the speciation modeling. The differences observed in the copper species distribution between that of the fish gill microenvironment and the surrounding water were based on the speciation modeling. The change in copper bioavailability for fish uptake was also examined. The results indicate the presence of an experimental pH balance point at 6.9, where the pH in the fish gill microenvironment is identical to that of the surrounding water. The observed deviation range in pH levels between that found at the gills and that of the surrounding water varied from -0.4 to 0.8 units. A sinusoidal model was developed for calculation of gill pH based on the pH of the surrounding water. Models calculating alkalinity either in the gill microenvironment or in the surrounding water and for estimating mucus secretion were also developed. The results of the chemical equilibrium calculations demonstrate that, within a pH range of 6-9, the dominant species of copper in bulk solution shifted from free ions to that of the hydroxo complex. With respect to the fish gill microenvironment, the dominant species found under acidic conditions were the mucus copper complex and free ions. Because of the influence of mucus complexation and pH change, bioavailable copper species in the fish gill

  15. 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

  16. 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.

  17. 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

  18. Speciation and quantification of vapor phases in soy biodiesel and waste cooking oil biodiesel.

    PubMed

    Peng, Chiung-Yu; Lan, Cheng-Hang; Dai, Yu-Tung

    2006-12-01

    This study characterizes the compositions of two biodiesel vapors, soy biodiesel and waste cooking oil biodiesel, to provide a comprehensive understanding of biodiesels. Vapor phases were sampled by purging oil vapors through thermal desorption tubes which were then analyzed by the thermal desorption/GC/MS system. The results show that the compounds of biodiesel vapors can be divided into four groups. They include methyl esters (the main biodiesel components), oxygenated chemicals, alkanes and alkenes, and aromatics. The first two chemical groups are only found in biodiesel vapors, not in the diesel vapor emissions. The percentages of mean concentrations for methyl esters, oxygenated chemicals, alkanes and alkenes, and aromatics are 66.1%, 22.8%, 4.8% and 6.4%, respectively for soy biodiesel, and 35.8%, 35.9%, 27.9% and 0.3%, respectively for waste cooking oil biodiesel at a temperature of 25+/-2 degrees C. These results show that biodiesels have fewer chemicals and lower concentrations in vapor phase than petroleum diesel, and the total emission rates are between one-sixteenth and one-sixth of that of diesel emission, corresponding to fuel evaporative emissions of loading losses of between 106 microg l(-1) and 283 microg l(-1). Although diesels generate more vapor phase emissions, biodiesels still generate considerable amount of vapor emissions, particularly the emissions from methyl esters and oxygenated chemicals. These two chemical groups are more reactive than alkanes and aromatics. Therefore, speciation and quantification of biodiesel vapor phases are important. PMID:16904162

  19. Speciation of mercury compounds by differential atomization - atomic absorption spectroscopy

    SciTech Connect

    Robinson, J.W.; Skelly, E.M.

    1982-01-01

    This paper describes the dual stage atomization technique which allows speciation of several mercury-containing compounds in aqueous solution and in biological fluids. The technique holds great promise for further speciation studies. Accurate temperature control, expecially at temperatures less than 200/sup 0/C, is needed to separate the extremely volatile mercury halides and simple organomercurials from each other. Studies with mercury salts and EDTA, L-cysteine and dithioxamide demonstrate that this technique may be used to study the extent of complex formation. Investigations of biological fluids indicate that there is a single predominant form of mercury in sweat and a single predominant form of mercury in urine. The mercury compound in urine is more volatile than that in sweat. Both quantitative and qualitative analyses are possible with this technique.

  20. 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.

  1. Hybridization Reveals the Evolving Genomic Architecture of Speciation

    PubMed Central

    Kronforst, Marcus R.; Hansen, Matthew E.B.; Crawford, Nicholas G.; Gallant, Jason R.; Zhang, Wei; Kulathinal, Rob J.; Kapan, Durrell D.; Mullen, Sean P.

    2014-01-01

    SUMMARY The rate at which genomes diverge during speciation is unknown, as are the physical dynamics of the process. Here, we compare full genome sequences of 32 butterflies, representing five species from a hybridizing Heliconius butterfly community, to examine genome-wide patterns of introgression and infer how divergence evolves during the speciation process. Our analyses reveal that initial divergence is restricted to a small fraction of the genome, largely clustered around known wing-patterning genes. Over time, divergence evolves rapidly, due primarily to the origin of new divergent regions. Furthermore, divergent genomic regions display signatures of both selection and adaptive introgression, demonstrating the link between microevolutionary processes acting within species and the origin of species across macroevolutionary timescales. Our results provide a uniquely comprehensive portrait of the evolving species boundary due to the role that hybridization plays in reducing the background accumulation of divergence at neutral sites. PMID:24183670

  2. 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).

  3. 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

  4. 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. PMID:25724950

  5. Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

    NASA Astrophysics Data System (ADS)

    Deng, Yamin; Nordstrom, D. Kirk; Blaine McCleskey, R.

    2011-08-01

    Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1-10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006-2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H + and Al 3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3-30% for more than 90% of samples at or above 10 -6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F -, and major complexes ( HF(aq)0, AlF 2+, AlF2+ and AlF30) account for more than 95% of total fluoride. Occasionally, some complex species like AlF4-, FeF 2+, FeF2+, MgF + and BF(OH)2- may comprise 1-10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.

  6. Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

    USGS Publications Warehouse

    Deng, Y.; Nordstrom, D.K.; Blaine, McCleskey R.

    2011-01-01

    Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1-10), temperature, and high concentrations of fluoride (up to 50mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50??C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006-2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H+ and Al3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3-30% for more than 90% of samples at or above 10-6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F-, and major complexes (HF(aq)0, AlF2+, AlF2+ and AlF30) account for more than 95% of total fluoride. Occasionally, some complex species like AlF4-, FeF2+, FeF2+, MgF+ and BF2(OH)2- may comprise 1-10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al. ?? 2011.

  7. How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

    NASA Astrophysics Data System (ADS)

    Kam, K.; Lemke, K.

    2014-12-01

    The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with

  8. Pu speciation in actual and simulated aged wastes

    SciTech Connect

    Lezama-pacheco, Juan S; Conradson, Steven D

    2008-01-01

    X-ray Absorption Fine Structure Spectroscopy (XAFS) at the Pu L{sub II/III} edge was used to determine the speciation of this element in (1) Hanford Z-9 Pu crib samples, (2) deteriorated waste resins from a chloride process ion-exchange purification line, and (3) the sediments from two Waste Isolation Pilot Plant Liter Scale simulant brine systems. The Pu speciation in all of these samples except one is within the range previously displayed by PuO{sub 2+x-2y}(OH){sub y}{center_dot}zH{sub 2}O compounds, which is expected based on the putative thermodynamic stability of this system for Pu equilibrated with excess H{sub 2}O and O{sub 2} under environmental conditions. The primary exception was a near neutral brine experiment that displayed evidence for partial substitution of the normal O-based ligands with Cl{sup -} and a concomitant expansion of the Pu-Pu distance relative to the much more highly ordered Pu near neighbor shell in PuO{sub 2}. However, although the Pu speciation was not necessarily unusual, the Pu chemistry identified via the history of these samples did exhibit unexpected patterns, the most significant of which may be that the presence of the Pu(V)-oxo species may decrease rather than increase the overall solubility of these compounds. Several additional aspects of the Pu speciation have also not been previously observed in laboratory-based samples. The molecular environmental chemistry of Pu is therefore likely to be more complicated than would be predicted based solely on the behavior of PuO{sub 2} under laboratory conditions.

  9. Can natural levels of Al influence Cu speciation and toxicity to Daphnia magna in a Swedish soft water lake?

    PubMed

    Hoppe, S; Gustafsson, J-P; Borg, H; Breitholtz, M

    2015-11-01

    It is well known that chemical parameters, such as natural organic matter (NOM), cation content and pH may influence speciation and toxicity of metals in freshwaters. Advanced bioavailability models, e.g. Biotic Ligand Models (BLMs), can use these and other chemical parameters to calculate site specific recommendations for metals in the aquatic environment. However, since Al is not an input parameter in the BLM v.2.2.3, used in this study, there could be a discrepancy between calculated and measured results in Al rich waters. The aim of this study was to evaluate if the presence of Al in a circumneutral (pH ∼6) soft humic freshwater, Lake St. Envättern, will affect the Cu speciation and thereby the toxicity to the cladoceran Daphnia magna. The results show a statistically significant increase in the free Cu(2+) concentration with Al additions and that measured levels of Cu(2+) significantly differed from BLM calculated levels of Cu(2+). Furthermore, there was also a statistically significant elevated acute toxic response to D. magna at low additions of Al (10 μg/L). However, since the large difference between calculated and measured Cu(2+) resulted in a significant but minor (factor of 2.3) difference between calculated and measured toxicity, further studies should be conducted in Al rich soft waters to evaluate the importance of adding Al as an input parameter into the BLM software. PMID:26073589

  10. Optimization and Application of APCI Hydrogen-Deuterium Exchange Mass Spectrometry (HDX MS) for the Speciation of Nitrogen Compounds

    NASA Astrophysics Data System (ADS)

    Acter, Thamina; Cho, Yunju; Kim, Sungji; Ahmed, Arif; Kim, Byungjoo; Kim, Sunghwan

    2015-09-01

    A systematic study was performed to investigate the utility of atmospheric pressure chemical ionization hydrogen-deuterium exchange mass spectrometry (APCI HDX MS) to identify the structures of nitrogen-containing aromatic compounds. First, experiments were performed to determine the optimized experimental conditions, with dichloromethane and CH3OD found to be good cosolvents for APCI HDX. In addition, a positive correlation between the heated capillary temperature and the observed HDX signal was observed, and it was suggested that the HDX reaction occurred when molecules were contained in the solvent cluster. Second, 20 standard nitrogen-containing compounds were analyzed to investigate whether speciation could be determined based on the different types of ions produced from nitrogen-containing compounds with various functional groups. The number of exchanges occurring within the compounds correlated well with the number of active hydrogen atoms attached to nitrogen, and it was confirmed that APCI HDX MS could be used to determine speciation. The results obtained by APCI HDX MS were combined with the subsequent investigation of the double bond equivalence distribution and indicated that resins of shale oil extract contained mostly pyridine type nitrogen compounds. This study confirmed that APCI HDX MS can be added to previously reported chemical ionization, electrospray ionization, and atmospheric pressure photo ionization-based HDX methods, which can be used for structural elucidation by mass spectrometry.

  11. Optimization and Application of APCI Hydrogen-Deuterium Exchange Mass Spectrometry (HDX MS) for the Speciation of Nitrogen Compounds.

    PubMed

    Acter, Thamina; Cho, Yunju; Kim, Sungji; Ahmed, Arif; Kim, Byungjoo; Kim, Sunghwan

    2015-09-01

    A systematic study was performed to investigate the utility of atmospheric pressure chemical ionization hydrogen-deuterium exchange mass spectrometry (APCI HDX MS) to identify the structures of nitrogen-containing aromatic compounds. First, experiments were performed to determine the optimized experimental conditions, with dichloromethane and CH(3)OD found to be good cosolvents for APCI HDX. In addition, a positive correlation between the heated capillary temperature and the observed HDX signal was observed, and it was suggested that the HDX reaction occurred when molecules were contained in the solvent cluster. Second, 20 standard nitrogen-containing compounds were analyzed to investigate whether speciation could be determined based on the different types of ions produced from nitrogen-containing compounds with various functional groups. The number of exchanges occurring within the compounds correlated well with the number of active hydrogen atoms attached to nitrogen, and it was confirmed that APCI HDX MS could be used to determine speciation. The results obtained by APCI HDX MS were combined with the subsequent investigation of the double bond equivalence distribution and indicated that resins of shale oil extract contained mostly pyridine type nitrogen compounds. This study confirmed that APCI HDX MS can be added to previously reported chemical ionization, electrospray ionization, and atmospheric pressure photo ionization-based HDX methods, which can be used for structural elucidation by mass spectrometry. PMID:26115964

  12. Selenium speciation in framboidal and euhedral pyrites in shales.

    PubMed

    Matamoros-Veloza, Adriana; Peacock, Caroline L; Benning, Liane G

    2014-08-19

    The release of Se from shales is poorly understood because its occurrence, distribution, and speciation in the various components of shale are unknown. To address this gap we combined bulk characterization, sequential extractions, and spatially resolved μ-focus spectroscopic analyses and investigated the occurrence and distribution of Se and other associated elements (Fe, As, Cr, Ni, and Zn) and determined the Se speciation at the μ-scale in typical, low bulk Se containing shales. Our results revealed Se primarily correlated with the pyrite fraction with exact Se speciation highly dependent on pyrite morphology. In euhedral pyrites, we found Se(-II) substitutes for S in the mineral structure. However, we also demonstrate that Se is associated with framboidal pyrite grains as a discrete, independent FeSex phase. The presence of this FeSex species has major implications for Se release, because FeSex species oxidize much faster than Se substituted in the euhedral pyrite lattice. Thus, such an FeSex species will enhance and control the dynamics of Se weathering and release into the aqueous environment. PMID:25032506

  13. Arsenic concentration and speciation in infant formulas and first foods

    PubMed Central

    Jackson, Brian P.; Taylor, Vivien F.; Punshon, Tracy; Cottingham, Kathryn L.

    2012-01-01

    Arsenic exposure to humans is pervasive, and, increasingly, studies are revealing adverse health effects at ever lower doses. Drinking water is the main route of exposure for many individuals; however, food can be a significant source of arsenic to an individual, especially if their diet is rice-based. Infants are particularly susceptible to dietary exposure, since many first foods contain rice and they have a low body mass. Here we report on arsenic concentration and speciation in infant formulas and first foods. Speciation is essential for food analysis because of the much greater toxicity of inorganic arsenic species and the possibility that arsenic in food (unlike water) may be present in either inorganic or organic forms. Infant milk formulas were low in total arsenic (2.2–12.6 ng g−1, n=15). Non-dairy formulas were significantly higher in arsenic than dairy-based formulas. Arsenic in formula was almost exclusively inorganic and predominantly arsenic(V). Arsenic concentration in purees (n=41) and stage 3 foods (n=18) ranged from 0.3–22 ng g−1. Rice-fortified foods had significantly higher total arsenic concentrations than non rice-based foods. Again arsenic speciation was predominantly inorganic; arsenic(III) was the main species with lower concentrations of DMA and arsenic(V) also present. These data confirm that infants are exposed to arsenic via diet, and suggest that careful attention to diet choices may limit this. PMID:22701232

  14. Silver speciation in wastewater effluent, surface waters, and pore waters

    SciTech Connect

    Adams, N.W.H.; Kramer, J.R.

    1999-12-01

    Silver, inorganic sulfide, and thiol compounds were measured in municipal wastewater effluent, receiving waters, and pore waters from an anoxic lake sediment in order to predict silver speciation in these systems. The authors found submicromolar concentrations of inorganic sulfide even in fully oxic surface water. This inorganic sulfide is likely to exist in the form of colloidal metal sulfides, which have been shown to be stable under oxidizing conditions for periods of several hours. Inorganic sulfide in both the wastewater effluent and receiving waters was found to be 200 to 300 times in excess of silver concentrations, whereas inorganic sulfide in pore waters was 1,000 to 15,000 times in excess of silver concentrations. With sulfide in excess of silver, the authors predict silver sulfide complexes to dominate silver speciation. Thiols were present at low nanomolar levels in pore waters but were not detectable in wastewater effluent or receiving waters. Thiols do not appear to be important to silver speciation in these freshwater systems. Partitioning of silver into particular, colloidal, and dissolved size fractions showed that a significant proportion of silver is in the colloidal and dissolved phases. Dissolved phase concentrations were relatively constant in the treatment plant effluent and receiving waters, suggesting that silver in the <10-kDa size fraction is strongly complexed by ligands that are not significantly affected by aggregation or sorption processes.

  15. Recent advances in arsenic bioavailability, transport, and speciation in rice.

    PubMed

    Wang, Xin; Peng, Bo; Tan, Changyin; Ma, Lena; Rathinasabapathi, Bala

    2015-04-01

    Widespread arsenic (As) contamination in paddy rice (Oryza sativa) from both geologic and anthropogenic origins is an increasing concern globally. Substantial efforts have been made to elucidate As transformation and uptake processes in rhizosphere and metabolism in rice plant, which provides an essential foundation for the development of mitigation strategies. However, a range of crucial mechanisms from As mobilization in rhizosphere to transport to grains remain poorly understood. To provide new insight into the underlying mechanisms of As accumulation in rice, a range of new perspectives on As bioavailability, transport pathways, and in situ speciation are reviewed here. Specifically, the prominent effects of water regime, Fe plaque, and biochar on As mobilization in rice rhizosphere are discussed critically. An updated understanding of arsenite (AsIII) and methylated As transport from root to vascular bundle and grain is integrated and discussed in detail. Special attention is given to As speciation and distribution in rice grain with potential coping strategies being provided and discussed. Future research priorities are also identified. The new insight into As bioavailability, transport and speciation in rice would lead to a better understanding of As contamination in rice. They would also provide useful strategies from agronomic measures to genetic engineering for more effective restriction of As transport and accumulation in food chain. PMID:25827791

  16. Tree of Life Reveals Clock-Like Speciation and Diversification

    PubMed Central

    Hedges, S. Blair; Marin, Julie; Suleski, Michael; Paymer, Madeline; Kumar, Sudhir

    2015-01-01

    Genomic data are rapidly resolving the tree of living species calibrated to time, the timetree of life, which will provide a framework for research in diverse fields of science. Previous analyses of taxonomically restricted timetrees have found a decline in the rate of diversification in many groups of organisms, often attributed to ecological interactions among species. Here, we have synthesized a global timetree of life from 2,274 studies representing 50,632 species and examined the pattern and rate of diversification as well as the timing of speciation. We found that species diversity has been mostly expanding overall and in many smaller groups of species, and that the rate of diversification in eukaryotes has been mostly constant. We also identified, and avoided, potential biases that may have influenced previous analyses of diversification including low levels of taxon sampling, small clade size, and the inclusion of stem branches in clade analyses. We found consistency in time-to-speciation among plants and animals, ∼2 My, as measured by intervals of crown and stem species times. Together, this clock-like change at different levels suggests that speciation and diversification are processes dominated by random events and that adaptive change is largely a separate process. PMID:25739733

  17. The genetics of speciation: Insights from Fisher's geometric model.

    PubMed

    Fraïsse, Christelle; Gunnarsson, P Alexander; Roze, Denis; Bierne, Nicolas; Welch, John J

    2016-07-01

    Research in speciation genetics has uncovered many robust patterns in intrinsic reproductive isolation, and fitness landscape models have been useful in interpreting these patterns. Here, we examine fitness landscapes based on Fisher's geometric model. Such landscapes are analogous to models of optimizing selection acting on quantitative traits, and have been widely used to study adaptation and the distribution of mutational effects. We show that, with a few modifications, Fisher's model can generate all of the major findings of introgression studies (including "speciation genes" with strong deleterious effects, complex epistasis and asymmetry), and the major patterns in overall hybrid fitnesses (including Haldane's Rule, the speciation clock, heterosis, hybrid breakdown, and male-female asymmetry in the F1). We compare our approach to alternative modeling frameworks that assign fitnesses to genotypes by identifying combinations of incompatible alleles. In some cases, the predictions are importantly different. For example, Fisher's model can explain conflicting empirical results about the rate at which incompatibilities accumulate with genetic divergence. In other cases, the predictions are identical. For example, the quality of reproductive isolation is little affected by the manner in which populations diverge. PMID:27252049

  18. Signals and speciation in plant-feeding insects

    NASA Astrophysics Data System (ADS)

    Cocroft, Reginald; Rodriguez, Rafael; Hunt, Randy

    2003-04-01

    Communication can play a role in speciation when differences in signaling systems reduce gene flow between diverging lineages. However, the observation that closely related species have different signals leaves open the question of cause and effect, because divergence in signals can also occur after speciation is completed. The relationship of signals and divergence is being investigated in the Enchenopa binotata species complex of treehoppers, a group of plant-feeding insects that communicate using substrate-borne vibrational signals. Speciation in the E. binotata complex is hypothesized to have resulted from repeated shifts to novel host plants. Sources of selection on the signals of these treehoppers can be studied not only in fully differentiated species, but also in experimental populations in the early stages of divergence. Some unique features of vibrational communication through plant stems will be discussed, as well as how shifts to novel host plants may influence signaling systems, and what role(s) communication may have played in the process of evolutionary divergence in this group.

  19. Speciation with gene flow and the genetics of habitat transitions.

    PubMed

    Cristescu, Melania E; Constantin, Anna; Bock, Dan G; Cáceres, Carla E; Crease, Teresa J

    2012-03-01

    Whether speciation can advance to completion in the face of initially high levels of gene flow is a very controversial topic in evolutionary biology. Extensive gene exchange is generally considered to homogenize populations and counteract divergence. Moreover, the role of introgressive hybridization in evolution remains largely unexplored in animals, particularly in freshwater zooplankton in which allopatric speciation is considered to be the norm. Our work investigates the genetic structure of two young ecological species: the pond species, Daphnia pulex and the lake species, Daphnia pulicaria. Phylogenetic and population genetics analyses were conducted on mitochondrial NADH dehydrogenase 5 (ND5) gene, the nuclear Lactate dehydrogenase (Ldh) gene and 21 nuclear microsatellite markers in 416 individuals from habitats with various degrees of permanence. The strong and consistent phylogenetic discordance between nuclear and mitochondrial markers suggests a complex evolutionary history of multiple independent habitat transition events that involved hybridization and introgression between lake and pond Daphnia. On the other hand, the low level of contemporary gene flow between adjacent populations indicates the presence of effective habitat isolating barriers. The Daphnia system provides strong evidence for a divergence-with-gene flow speciation model that involves multiple habitat transition events. PMID:22269101

  20. Introduction. Speciation in plants and animals: pattern and process.

    PubMed

    Abbott, Richard J; Ritchie, Michael G; Hollingsworth, Peter M

    2008-09-27

    Although approximately 150 years have passed since the publication of On the origin of species by means of natural selection, the definition of what species are and the ways in which species originate remain contentious issues in evolutionary biology. The biological species concept, which defines species as groups of interbreeding natural populations that are reproductively isolated from other such groups, continues to draw support. However, there is a growing realization that many animal and plant species can hybridize with their close relatives and exchange genes without losing their identity. On occasion, such hybridization can lead to the origin of new species. A key to understanding what species are and the ways in which they originate rests to a large extent on a detailed knowledge of the nature and genetics of factors that limit gene flow between species and the conditions under which such isolation originates. The collection of papers in this issue addresses these topics and deals as well with some specific issues of hybrid speciation and the causes of species radiations. The papers included arise from a 1-day symposium on speciation held during the Sixth Biennial Meeting of the Systematics Association at Edinburgh in August 2007. In this introduction, we provide some background to these papers and highlight some key points made. The papers make clear that highly significant advances to our understanding of animal and plant speciation are currently being made across the range of this topic. PMID:18583278

  1. Iron Speciation in the Subtropical Waters East of New Zealand using Multi Detection Window CLE-AdCSV Titrations.

    NASA Astrophysics Data System (ADS)

    Chandrasekhar, Anoop; Sander, Sylvia; Milnes, Angie; Boyd, Philip

    2015-04-01

    ). "Chemical speciation of iron in seawater using catalytic cathodic stripping voltammetry with ligand competition against salicylaldoxime." Marine Chemistry 164(0): 60-74. Buck, K. N., J. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo and J. Wu (2012). "The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques " Limnology and Oceanography: Methods 10: 496-515. Hudson, R. J. M., E. L. Rue and K. W. Bruland (2003). "Modeling Complexometric Titrations of Natural Water Samples." Environ. Sci. Tech. 37: 1553-1562. Pizeta, I., S. G. Sander, O. Baars, K. Buck, R. Bundy, G. Carrasco, P. Croot, C. Garnier, L. Gerringa, M. Gledhill, K. Hirose, D. R. Hudson, Y. Kondo-Jacquot, L. Laglera, D. Omanovic, M. Rijkenberg, B. Twining and M. Wells (in preparation). "Intercomparison of estimating metal binding ligand parameters from simulated titration data using different fitting approaches." for Limnology and Oceanography: Methods. Sander, S. G., K. A. Hunter, H. Harms and M. Wells (2011). "Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability." Environmental Science and Technology 45(15): 6388-6395.

  2. Atmospheric mercury speciation in Yellowstone National Park

    USGS Publications Warehouse

    Hall, B.D.; Olson, M.L.; Rutter, A.P.; Frontiera, R.R.; Krabbenhoft, D.P.; Gross, D.S.; Yuen, M.; Rudolph, T.M.; Schauer, J.J.

    2006-01-01

    Atmospheric concentrations of elemental mercury (Hg0), reactive gaseous Hg (RGM), and particulate Hg (pHg) concentrations were measured in Yellowstone National Park (YNP), U.S.A. using high resolution, real time atmospheric mercury analyzers (Tekran 2537A, 1130, and 1135). A survey of Hg0 concentrations at various locations within YNP showed that concentrations generally reflect global background concentrations of 1.5-2.0 ng m- 3, but a few specific locations associated with concentrated geothermal activity showed distinctly elevated Hg0 concentrations (about 9.0 ng m- 3). At the site of intensive study located centrally in YNP (Canyon Village), Hg0 concentrations did not exceed 2.5 ng m- 3; concentrations of RGM were generally below detection limits of 0.88 pg m- 3 and never exceeded 5 pg m- 3. Concentrations of pHg ranged from below detection limits to close to 30 pg m-3. RGM and pHg concentrations were not correlated with any criteria gases (SO2, NOx, O3); however pHg was weakly correlated with the concentration of atmospheric particles. We investigated three likely sources of Hg at the intensive monitoring site: numerous geothermal features scattered throughout YNP, re-suspended soils, and wildfires near or in YNP. We examined relationships between the chemical properties of aerosols (as measured using real time, single particle mass spectrometry; aerosol time-of-flight mass spectrometer; ATOFMS) and concentrations of atmospheric pHg. Based on the presence of particles with distinct chemical signatures of the wildfires, and the absence of signatures associated with the other sources, we concluded that wildfires in the park were the main source of aerosols and associated pHg to our sampling site. ?? 2005 Elsevier B.V. All rights reserved.

  3. Rapid and Extensive Alteration of Phosphorus Speciation during Oxic Storage of Wet Sediment Samples

    PubMed Central

    Kraal, Peter; Slomp, Caroline P.

    2014-01-01

    The chemical forms of phosphorus (P) in sediments are routinely measured in studies of P in modern and ancient marine environments. However, samples for such analyses are often exposed to atmospheric oxygen during storage and handling. Recent work suggests that long-term exposure of pyrite-bearing sediments can lead to a decline in apatite P and an increase in ferric Fe-bound P. Here, we report on alterations in P speciation in reducing modern Baltic Sea sediments that we deliberately exposed to atmospheric oxygen for a period of either one week or one year. During oxidation of the sediment, extensive changes occurred in all measured P reservoirs. Exchangeable P all but disappeared during the first week of exposure, likely reflecting adsorption of porewater PO4 by Fe(III) (oxyhydr)oxides (i.e. ferric Fe-bound P formation). Detrital and organic P were also rapidly affected: decreases in both reservoirs were already observed after the first week of exposure to atmospheric oxygen. This was likely because of acidic dissolution of detrital apatite and oxidation of organic matter, respectively. These processes produced dissolved PO4 that was then scavenged by Fe(III) (oxyhydr)oxides. Interestingly, P in authigenic calcium phosphates (i.e. apatite: authigenic Ca-P) remained unaffected after the first week of exposure, which we attributed to the shielding effect of microfossils in which authigenic Ca-P occurs in Baltic Sea sediments. This effect was transient; a marked decrease in the authigenic Ca-P pool was observed in the sediments after one year of exposure to oxygen. In summary, we show that handling and storage of wet sediments under oxic conditions can lead to rapid and extensive alteration of the original sediment P speciation. PMID:24802813

  4. Simultaneous Electrodialytic Preconcentration and Speciation of Chromium(III) and Chromium(VI).

    PubMed

    Ohira, Shin-Ichi; Nakamura, Koretaka; Shelor, C Phillip; Dasgupta, Purnendu K; Toda, Kei

    2015-11-17

    Large amounts of chromium (Cr) compounds are used for manufacturing of various products and various chemical processes. Some inevitably find their way into the environment. Environmental Cr is dominantly inorganic and is either in the cationic +3 oxidation state or in the anionic oxochromium +6 oxidation state. The two differ dramatically in their implications; Cr(III) is essential to human nutrition and even sold as a supplement, while Cr(VI) is a potent carcinogen. Drinking water standards for chromium may be based on total Cr or Cr(VI) only. Thus, Cr speciation analysis is very important. Despite their high sensitivity, atomic spectrometric techniques or induction coupled plasma-mass spectrometry (ICP-MS) cannot directly differentiate the oxidation states. We present here a new electrodialytic separation concept. Sample analyte ions are quantitatively transferred via appropriately ionically functionalized dialysis membranes into individual receptors that are introduced into the ICP-MS. There was no significant conversion of Cr(VI) to Cr(III) or vice versa during the very short (6 s) separation process. Effects of salinity (up to ∼20 mM NaCl) can be eliminated with proper membrane functionalization and receptor optimization. With the ICP-MS detector we used, the limits of detection for either form of Cr was 0.1 μg/L without preconcentration. Up to 10-fold preconcentration was readily possible by increasing the donor solution flow rate relative to the acceptor solution flow rates. The proposed approach permits simultaneous matrix isolation, preconcentration, and chromium speciation. PMID:26507203

  5. Speciation, characterization, and mobility of As, Se, and Hg in flue gas desulphurization residues.

    PubMed

    Al-Abed, Souhail R; Jegadeesan, Gautham; Scheckel, Kirk G; Tolaymat, Thabet

    2008-03-01

    Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se), and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue. With increasing reuse of the FGD residues in beneficial applications, it is important to determine metal speciation and mobilityto understand the environmental impact of its reuse. In this paper, we report the solid phase speciation of As, Se, and Hg in FGD residues using X-ray absorption spectroscopy (XAS), X-ray fluorescence spectroscopy (XRF), and sequential chemical extraction (SCE) techniques. The SCE results combined with XRF data indicated a strong possibility of As association with iron oxides, whereas Se was distributed among all geochemical phases. Hg appeared to be mainly distributed in the strong-complexed phase. XRF images also suggested a strong association of Hg with Fe oxide materials within FGD residues. XAS analysis indicated that As existed in its oxidized state (As(V)), whereas Se and Hg was observed in primarily reduced states as selenite (Se(IV)) and Hg(I), respectively. The results from the SCE and variable pH leaching tests indicated that the labile fractions of As, Se, and Hg were fairly low and thus suggestive of their stability in the FGD residues. However, the presence of a fine fraction enriched in metal content in the FGD residue suggested that size fractionation is important in assessing the environmental risks associated with their reuse. PMID:18441822

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

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Catalano, Jeffrey G.

    2012-08-01

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

  7. Rapid and extensive alteration of phosphorus speciation during oxic storage of wet sediment samples.

    PubMed

    Kraal, Peter; Slomp, Caroline P

    2014-01-01

    The chemical forms of phosphorus (P) in sediments are routinely measured in studies of P in modern and ancient marine environments. However, samples for such analyses are often exposed to atmospheric oxygen during storage and handling. Recent work suggests that long-term exposure of pyrite-bearing sediments can lead to a decline in apatite P and an increase in ferric Fe-bound P. Here, we report on alterations in P speciation in reducing modern Baltic Sea sediments that we deliberately exposed to atmospheric oxygen for a period of either one week or one year. During oxidation of the sediment, extensive changes occurred in all measured P reservoirs. Exchangeable P all but disappeared during the first week of exposure, likely reflecting adsorption of porewater PO4 by Fe(III) (oxyhydr)oxides (i.e. ferric Fe-bound P formation). Detrital and organic P were also rapidly affected: decreases in both reservoirs were already observed after the first week of exposure to atmospheric oxygen. This was likely because of acidic dissolution of detrital apatite and oxidation of organic matter, respectively. These processes produced dissolved PO4 that was then scavenged by Fe(III) (oxyhydr)oxides. Interestingly, P in authigenic calcium phosphates (i.e. apatite: authigenic Ca-P) remained unaffected after the first week of exposure, which we attributed to the shielding effect of microfossils in which authigenic Ca-P occurs in Baltic Sea sediments. This effect was transient; a marked decrease in the authigenic Ca-P pool was observed in the sediments after one year of exposure to oxygen. In summary, we show that handling and storage of wet sediments under oxic conditions can lead to rapid and extensive alteration of the original sediment P speciation. PMID:24802813

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

    SciTech Connect

    Frierdich, Andrew J.; Catalano, Jeffrey G.

    2012-10-24

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

  9. Speciation, Characterization and Mobility of As, Se and Hg in Flue Gas Desulphurization Residues

    SciTech Connect

    Al-Abed, S.R.; Jegadeesan, G.; Scheckel, K.G.; Tolaymat, T.

    2008-06-23

    Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se), and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue. With increasing reuse of the FGD residues in beneficial applications, it is important to determine metal speciation and mobility to understand the environmental impact of its reuse. In this paper, we report the solid phase speciation of As, Se, and Hg in FGD residues using X-ray absorption spectroscopy (XAS), X-ray fluorescence spectroscopy (XRF), and sequential chemical extraction (SCE) techniques. The SCE results combined with XRF data indicated a strong possibility of As association with iron oxides, whereas Se was distributed among all geochemical phases. Hg appeared to be mainly distributed in the strong-complexed phase. XRF images also suggested a strong association of Hg with Fe oxide materials within FGD residues. XAS analysis indicated that As existed in its oxidized state (As(V)), whereas Se and Hg was observed in primarily reduced states as selenite (Se(IV)) and Hg(I), respectively. The results from the SCE and variable pH leaching tests indicated that the labile fractions of As, Se, and Hg were fairly low and thus suggestive of their stability in the FGD residues. However, the presence of a fine fraction enriched in metal content in the FGD residue suggested that size fractionation is important in assessing the environmental risks associated with their reuse.

  10. Speciation, characterization, and mobility of As, Se, and Hg in flue gas desulphurization residues

    SciTech Connect

    Souhail R. Al-Abed; Gautham Jegadeesan; Kirk G. Scheckel; Thabet Tolaymat

    2008-03-01

    Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se), and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue. With increasing reuse of the FGD residues in beneficial applications, it is important to determine metal speciation and mobility to understand the environmental impact of its reuse. In this paper, we report the solid phase speciation of As, Se, and Hg in FGD residues using X-ray absorption spectroscopy (XAS), X-ray fluorescence spectroscopy (XRF), and sequential chemical extraction (SCE) techniques. The SCE results combined with XRF data indicated a strong possibility of As association with iron oxides, whereas Se was distributed among all geochemical phases. Hg appeared to be mainly distributed in the strong-complexed phase. XRF images also suggested a strong association of Hg with Fe oxide materials within FGD residues. XAS analysis indicated that As existed in its oxidized state (As(V)), whereas Se and Hg was observed in primarily reduced states as selenite (Se(IV)) and Hg(I), respectively. The results from the SCE and variable pH leaching tests indicated that the labile fractions of As, Se, and Hg were fairly low and thus suggestive of their stability in the FGD residues. However, the presence of a fine fraction enriched in metal content in the FGD residue suggested that size fractionation is important in assessing the environmental risks associated with their reuse. 34 refs., 3 figs., 4 tabs.

  11. Distribution and speciation of selenium in the black shale of the Dogger aquifer in the Poitiers Experimental Hydrogeological Site

    NASA Astrophysics Data System (ADS)

    Bassil, Joseph; Naveau, Aude; Di Tullo, Pamela; Grasset, Laurent; Bodin, Jacques; Razack, Moumtaz; Kazpard, Véronique

    2014-05-01

    Selenium (Se) is an element having the narrowest range between dietary deficiency and toxic concentrations. In the environment, selenium has four oxidation states (-II, 0, IV and VI) and has a complex biogeochemical cycle. The European and French legislations fixed 10 µg/L as safe upper limit in drinking water. In several French regions2, selenium concentrations above the limit were detected in groundwater. This poses a problem for local authorities which are obliged to stop the exploitation of many wells. In the north flank of the "Seuil du Poitou", Selenium concentrations above 10 ppb were measured in groundwater samples collected from five wells of the Poitiers Experimental Hydrogeological Site (SEH), which investigates a 100 m carbonate aquifer (Dogger). Total rock analysis applied on samples representing all the geological facies observed in the SEH show that selenium is concentrated in the black clays that fulfill some karst cavities; these clays are thought considered as the main selenium source in the Dogger Aquifer. The main objective of this work is to study the distribution and the speciation of selenium in the geological matrix and the release mechanisms of Se in order to provide quantifiable data to numerical modeling of selenium's reactive flows across the aquifer. The distribution and the speciation of selenium in these black clays were studied by applying parallel and sequential chemical extractions and by verifying the impact of these extractions on the solid dissolution and organic matter mobilization. In all the extractions, the total dissolved selenium was quantified using ICP-MS and the selenium speciation in the aqueous phase by HPLC-ICP-MS. Verifying the impact of the extractions on the solid dissolution and on the organic matter mobilization was performed by measuring Al, Si, Fe and Ca by AAS and the Total Organic Carbon TOC and by acquisition of XRD diffractograms of the solid residues. Our results showed that most of the selenium is

  12. Distribution and speciation of metals (Cu, Zn, Cd, and Pb) in agricultural and non-agricultural soils near a stream upriver from the Pearl River, China.

    PubMed

    Yang, Silin; Zhou, Dequn; Yu, Huayong; Wei, Rong; Pan, Bo

    2013-06-01

    The distribution and chemical speciation of typical metals (Cu, Zn, Cd and Pb) in agricultural and non-agricultural soils were investigated in the area of Nanpan River, upstream of the Pearl River. The investigated four metals showed higher concentrations in agricultural soils than in non-agricultural soils, and the site located in factory district contained metals much higher than the other sampling sites. These observations suggested that human activities, such as water irrigation, fertilizer and pesticide applications might have a major impact on the distribution of metals. Metal speciation analysis presented that Cu, Zn and Cd were dominated by the residual fraction, while Pb was dominated by the reducible fraction. Because of the low mobility of the metals in the investigated area, no remarkable difference could be observed between upstream and downstream separated by the factory site. PMID:23466733

  13. ISSUES IN SIMULATING ELEMENTAL MERCURY AIR/WATER EXCHANGE AND AQUEOUS MONOMETHYLMERCURY SPECIATION

    EPA Science Inventory

    This presentation focuses on two areas relevant to assessing the global fate and bioavailability of mercury: elemental mercury air/water exchange and aqueous environmental monomethylmercury speciation.

  14. Atmospheric speciation of mercury in two contrasting Southeastern US airsheds

    NASA Astrophysics Data System (ADS)

    Gabriel, Mark C.; Williamson, Derek G.; Brooks, Steve; Lindberg, Steve

    Simultaneous measurement of gaseous elemental, reactive gaseous, and fine particulate mercury took place in Tuscaloosa AL, (urban airshed) and Cove Mountain, TN (non-urban airshed) during the summers of 2002 and 2003. The objective of this research was to (1) summarize the temporal distribution of each mercury specie at each site and compare to other speciation data sets developed by other researchers and (2) provide insight into urban and non-urban mercury speciation effects using various statistical methods. Average specie concentrations were as follows: 4.05 ng m -3 (GEM), 13.6 pg m -3 (RGM), 16.4 pg m -3 (Hg-p) for Tuscaloosa; 3.20 ng m -3 (GEM), 13.6 pg m -3 (RGM), 9.73 pg m -3 (Hg-p) for Cove Mountain. As a result of urban airshed impacts, short periods of high concentration for all mercury species was common in Tuscaloosa. At Cove Mountain a consistent mid-day rise and evening drop for mercury species was found. This pattern was primarily the result of un-impacted physical boundary layer movement, although, other potential impacts were ambient photochemistry and air-surface exchange of mercury. Meteorological parameters that are known to heavily impact mercury speciation were similar for the study period for Tuscaloosa and Cove Mountain except for wind speed (m s -1), which was higher at Cove Mountain. For both sites statistically significant ( p<0.0001), inverse relationships existed between wind speed and Hg 0 concentration. A weaker windspeed-Hg 0 correlation existed for Tuscaloosa. By analyzing Hg concentration—wind speed magnitude change at both sites it was found that wind speed at Cove Mountain had a greater influence on Hg 0 concentration variability than Tuscaloosa by a factor of 3. Using various statistical tests, we concluded that the nature of Tuscaloosa's atmospheric mercury speciation was the result of typical urban airshed impacts. Cove Mountain showed atmospheric mercury speciation characteristics indicative of a non-urban area along with

  15. Low Cost CE-NMR with Microcoils for Chemical Detection

    SciTech Connect

    Adams, K; Klunder, G; Demas, V; Malba, V; Bernhardt, A; Evan, L; Harvey, C; Maxwell, R; Herberg, J L

    2009-01-08

    Understanding speciation in solids and solutions is important for environmental and toxicological purposes. Capillary electrophoresis (CE) is a simple rapid separation technique that can be used to identify species in solution. CE is particularly is well suited for rapid separations of metal containing samples. Direct on-capillary measurement of metal compound speciation can be obtained with nuclear magnetic resonance (NMR). The development of a low-cost microcoil CE-NMR system for in situ characterization of samples of interest is discussed. High precision laser lithography is used to produce copper sputtered microcoils that have comparable resistivity and quality factors to that of hand wound microcoils. A portable NMR system coupled with a CE system has the potential to identify chemical species in aqueous solutions. In addition, transient isotachophoresis can separate and pre-concentrate samples of interest to obtain separate chemical peaks for speciation by online NMR analysis. We are developing separation assays to determine the speciation of chemical complexes in solutions with minimal perturbation to the original sample equilibrium. On-line NMR measurements will be made downstream of the UV detector.

  16. Low Cost CE-NMR with Microcoils for Chemical Detection

    SciTech Connect

    Adams, K L; Klunder, G; Demas, V; Malba, V; Bernhardt, A; Evan, L; Harvey, C; Maxwell, R; Herberg, J

    2008-07-25

    Understanding speciation in solids and solutions is important for environmental and toxicological purposes. Capillary electrophoresis (CE) is a simple rapid separation technique that can be used to identify species in solution. CE is particularly is well suited for rapid separations of metal containing samples. Direct on-capillary measurement of metal compound speciation can be obtained with nuclear magnetic resonance (NMR). The development of a low-cost microcoil CE-NMR system for in situ characterization of samples of interest is discussed. High precision laser lithography is used to produce copper sputtered microcoils that have comparable resistivity and quality factors to that of hand wound microcoils. A portable NMR system coupled with a CE system has the potential to identify chemical species in aqueous solutions. In addition, transient isotachophoresis can separate and pre-concentrate samples of interest to obtain separate chemical peaks for speciation by online NMR analysis. We are developing separation assays to determine the speciation of chemical complexes in solutions with minimal perturbation to the original sample equilibrium. On-line NMR measurements will be made downstream of the UV detector.

  17. Bacterial activities driving arsenic speciation and solubility in marine sediments

    NASA Astrophysics Data System (ADS)

    Battaglia-Brunet, F.; Seby, F.; Crouzet, C.; Joulian, C.; Mamindy-Pajany, Y.; Guezennec, A. G.; Hurel, C.; Marmier, N.; Bataillard, P.

    2012-04-01

    Harbour and marina sediments represent particular environments, with high concentrations in organic carbon and pollutants. Over 50 million m3 of marine sediments are dredged every year in French maritime and commercial ports, to maintain the water depth suitable for navigation, and the most part of them is discharged in deeper sea zones. The present study aimed to elucidate, using a range of complementary approaches, the influence of bacterial activity on arsenic speciation and mobility in marina sediments. Two sites were considered: L'Estaque, impacted by metallurgical activities and by the commercial port of Marseille, and St-Mandrier, less polluted, affected by classical chemical pollutants associated to professional and recreational boating. Arsenic concentration was noticeably higher in l'Estaque sediment (200-350 mg/kg) than in St-Mandrier sediment (15-50 mg/kg). In the solid phases, As(III) was the dominant species in L'Estaque sediment, whereas As(V) was the main form in St Mandrier sediment. At both sites, arsenic was the major trace element detected in interstitial water. Free sulfide and thio-arsenic complexes were detected in the interstitial water of l'Estaque sediment, suggesting a role of sulfate-reduction bacterial activity on arsenic solubility. Anaerobic microcosm experiments confirmed this hypothesis, as stimulation of sulfate-reduction induced a dramatic increase of arsenic concentration in the liquid phase, linked to the formation of soluble thio-arsenic complexes. Nevertheless, microcosms performed in aerobic conditions showed that bacterial activity globally decreased the transfer of arsenic from the sediment toward the overlying water. A red-brown fine layer developed at the sediment-water interface. Altogether, these results suggest that the sediment-water interface zone and the close transition area between aerobic and anaerobic conditions host intense biogeochemical reactions involving As, Fe and S species. These reactions most probably

  18. Leaching for recovery of copper from municipal solid waste incineration fly ash: influence of ash properties and metal speciation.

    PubMed

    Lassesson, Henric; Fedje, Karin Karlfeldt; Steenari, Britt-Marie

    2014-08-01

    Recovery of metals occurring in significant amounts in municipal solid waste incineration fly ash, such as copper, could offer several advantages: a decreased amount of potentially mobile metal compounds going to landfill, saving of natural resources and a monetary value. A combination of leaching and solvent extraction may constitute a feasible recovery path for metals from municipal solid waste incineration fly ash. However, it has been shown that the initial dissolution and leaching is a limiting step in such a recovery process. The work described in this article was focused on elucidating physical and chemical differences between two ash samples with the aim of explaining the differences in copper release from these samples in two leaching methods. The results showed that the chemical speciation is an important factor affecting the release of copper. The occurrence of copper as phosphate or silicate will hinder leaching, while sulphate and chloride will facilitate leaching. PMID:25106538

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

    NASA Astrophysics Data System (ADS)

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

    We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on

  20. Observational Constraints on Terpene Oxidation with and without Anthropogenic Influence in the Amazon using Speciated Measurements from SV-TAG

    NASA Astrophysics Data System (ADS)

    Yee, L.; Isaacman, G. A.; Kreisberg, N. M.; Liu, Y.; McKinney, K. A.; de Sá, S. S.; Martin, S. T.; Alexander, M. L.; Palm, B. B.; Hu, W.; Campuzano Jost, P.; Day, D. A.; Jimenez, J. L.; Viegas, J.; Springston, S. R.; Wurm, F.; Ferreira De Brito, J.; Artaxo, P.; Manzi, A. O.; Machado, L.; Longo, K.; Oliveira, M. B.; Souza, R. A. F. D.; Hering, S. V.; Goldstein, A. H.

    2014-12-01

    Biogenic volatile organic compounds (BVOCs) from the Amazon forest represent the largest regional source of organic carbon emissions to the atmosphere. These BVOC emissions dominantly consist of volatile and semi-volatile terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). However, the oxidation pathways of these compounds are still not well understood, and are expected to differ significantly between "pristine" conditions, as is common in Amazonia, and polluted conditions caused by emissions from growing cities. Our focus is to elucidate how anthropogenic emissions influence BVOC chemistry and BSOA formation through speciated measurements of their oxidation products. We have deployed the Semi-Volatile Thermal desorption Aerosol Gas Chromatograph (SV-TAG) at the rural T3 site located west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon) 2014 field campaign to measure hourly concentrations of semi-volatile BVOCs and their oxidation products during the wet and dry seasons. Primary BVOC concentrations measured by the SV-TAG include sesquiterpenes and diterpenes, which have rarely been speciated with high time-resolution. We observe sesquiterpenes to be anti-correlated with ozone, indicative of sesquiterpene oxidation playing a major role in the regional oxidant budget. The role of sesquiterpenes in atmospheric SOA formation are of interest due to their high aerosol yields and high reactivity with ozone, relative to more commonly measured BVOCs (e.g. monoterpenes). We explore relative concentrations of sesquiterpenes and monoterpenes and their roles as precursors to SOA formation by combining SV-TAG measurements with those from an additional suite of VOC and particle measurements deployed in the Amazon. We also report the first ever hourly observations of the gas-particle partitioning of speciated terpene oxidation products in the Amazon

  1. Effects of ozonation on the speciation of dissolved iodine in artificial seawater.

    PubMed

    Sherrill, Johanna; Whitaker, Brent R; Wong, George T F

    2004-09-01

    Iodine in the form of iodide is required for synthesis of tri-iodothyronine and thyroxine in fish. Iodine chemical speciation in aliquots of raw artificial seawater mix was measured before, during, and after exposure for fixed time periods to air only and to concentrations of ozone required to achieve oxidation-reduction potentials typical of a protein skimmer (400 mV) and an ozone contact chamber (800 mV). Chemical species of iodine were also measured in tank water from a large, recirculating, ozonated aquarium system that has a low-grade incidence of thyroid lesions (e.g., thyroiditis, hyperplasia, adenoma, and adenocarcinoma) in its fish. With increasing exposure to ozone, concentrations of iodide and dissolved organic iodine (DOI) decreased, whereas iodate levels increased. As a result of exposure to 400 mV, iodide concentration dropped to less than half the amount found in raw artificial seawater mix. After exposure to 800 mV, initial iodide levels decreased by 67%, and DOI became undetectable, whereas iodate concentration increased by 155%, with no remarkable change in total iodine concentration. These results indicate ozone-induced conversions from iodide to iodate, and DOI to iodide or iodate (or both). Iodide and DOI were not detectable in the aquarium system's water samples. Ozonation of artificial seawater may alter the relative concentrations of iodine species in a closed tank system, so that iodide supplementation of the diet or tank water of captive teleosts and elasmobranchs living in ozonated seawater is advisable. PMID:15526890

  2. Integrative analyses unveil speciation linked to host plant shift in Spialia butterflies.

    PubMed

    Hernández-Roldán, Juan L; Dapporto, Leonardo; Dincă, Vlad; Vicente, Juan C; Hornett, Emily A; Šíchová, Jindra; Lukhtanov, Vladimir A; Talavera, Gerard; Vila, Roger

    2016-09-01

    Discovering cryptic species in well-studied areas and taxonomic groups can have profound implications in understanding eco-evolutionary processes and in nature conservation because such groups often involve research models and act as flagship taxa for nature management. In this study, we use an array of techniques to study the butterflies in the Spialia sertorius species group (Lepidoptera, Hesperiidae). The integration of genetic, chemical, cytogenetic, morphological, ecological and microbiological data indicates that the sertorius species complex includes at least five species that differentiated during the last three million years. As a result, we propose the restitution of the species status for two taxa often treated as subspecies, Spialia ali (Oberthür, 1881) stat. rest. and Spialia therapne (Rambur, 1832) stat. rest., and describe a new cryptic species Spialia rosae Hernández-Roldán, Dapporto, Dincă, Vicente & Vila sp. nov. Spialia sertorius (Hoffmannsegg, 1804) and S. rosae are sympatric and synmorphic, but show constant differences in mitochondrial DNA, chemical profiles and ecology, suggesting that S. rosae represents a case of ecological speciation involving larval host plant and altitudinal shift, and apparently associated with Wolbachia infection. This study exemplifies how a multidisciplinary approach can reveal elusive cases of hidden diversity. PMID:27393640

  3. A radioiodine speciation, deposition, and dispersion model with uncertainty propagation for the Oak Ridge dose reconstruction.

    PubMed

    Nair, S K; Apostoaei, A I; Hoffman, F O

    2000-04-01

    Between 1944 and 1956, radioactive 131I was released into the atmosphere from operations at the Oak Ridge National Laboratory in Oak Ridge, TN. The releases occurred from stacks and from building vents and openings in three different chemical forms: elemental, organic, and particulate. During their transport in the atmosphere, different forms of iodine react differently with other atmospheric chemicals and moisture, and are removed from the plume at different rates by the processes of dry and wet deposition. A modified Gaussian plume model was developed to address the processes of radioiodine speciation, deposition, depletion, and dispersion in the atmosphere, and to propagate uncertainties in input parameter values through to the ground-level concentrations of 131I in air. A unique approach was used to develop an implicitly correlated set of hourly meteorological parameters for any day of a month for each month of the year from ten years of available data between 1987 and 1996. The model was validated for both annual average and short-term releases. For the annual average releases, the predictions of ground-level concentrations of 131I from the model were within a factor of 2 of measured field data. For two of the three sets of available weekly data, the measurements fell within the 95% subjective confidence interval of model predictions. Predictions of ground-level air concentrations were made on an annual average basis for the entire period of release and on a short-term, episodic basis for a 1954 accident. PMID:10749523

  4. Speciation of selenium in stream insects using X-ray absorption spectroscopy

    SciTech Connect

    Ruwandi Andrahennadi; Mark Wayland; Ingrid J. Pickering

    2007-11-15

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the