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Sample records for speciation biological

  1. Speciation of arsenic in biological samples.

    Science.gov (United States)

    Mandal, Badal Kumar; Ogra, Yasumitsu; Anzai, Kazunori; Suzuki, Kazuo T

    2004-08-01

    Speciation of arsenicals in biological samples is an essential tool to gain insight into its distribution in tissues and its species-specific toxicity to target organs. Biological samples (urine, hair, fingernail) examined in the present study were collected from 41 people of West Bengal, India, who were drinking arsenic (As)-contaminated water, whereas 25 blood and urine samples were collected from a population who stopped drinking As contaminated water 2 years before the blood collection. Speciation of arsenicals in urine, water-methanol extract of freeze-dried red blood cells (RBCs), trichloroacetic acid treated plasma, and water extract of hair and fingernail was carried out by high-performance liquid chromatography (HPLC)-inductively coupled argon plasma mass spectrometry (ICP MS). Urine contained arsenobetaine (AsB, 1.0%), arsenite (iAs(III), 11.3), arsenate (iAs(V), 10.1), monomethylarsonous acid (MMA(III), 6.6), monomethylarsonic acid (MMA(V), 10.5), dimethylarsinous acid (DMA(III), 13.0), and dimethylarsinic acid (DMA(V), 47.5); fingernail contained iAs(III) (62.4%), iAs(V) (20.2), MMA(V) (5.7), DMA(III) (8.9), and DMA(V) (2.8); hair contained iAs(III) (58.9%), iAs(V) (34.8), MMA(V) (2.9), and DMA(V) (3.4); RBCs contained AsB (22.5%) and DMA(V) (77.5); and blood plasma contained AsB (16.7%), iAs(III) (21.1), MMA(V) (27.1), and DMA(V) (35.1). MMA(III), DMA(III), and iAs(V) were not found in any plasma and RBCs samples, but urine contained all of them. Arsenic in urine, fingernails, and hair are positively correlated with water As, suggesting that any of these measurements could be considered as a biomarker to As exposure. Status of urine and exogenous contamination of hair urgently need speciation of As in these samples, but speciation of As in nail is related to its total As (tAs) concentration. Therefore, total As concentrations of nails could be considered as biomarker to As exposure in the endemic areas.

  2. Speciation of arsenic in biological samples

    International Nuclear Information System (INIS)

    Mandal, Badal Kumar; Ogra, Yasumitsu; Anzai, Kazunori; Suzuki, Kazuo T.

    2004-01-01

    Speciation of arsenicals in biological samples is an essential tool to gain insight into its distribution in tissues and its species-specific toxicity to target organs. Biological samples (urine, hair, fingernail) examined in the present study were collected from 41 people of West Bengal, India, who were drinking arsenic (As)-contaminated water, whereas 25 blood and urine samples were collected from a population who stopped drinking As contaminated water 2 years before the blood collection. Speciation of arsenicals in urine, water-methanol extract of freeze-dried red blood cells (RBCs), trichloroacetic acid treated plasma, and water extract of hair and fingernail was carried out by high-performance liquid chromatography (HPLC)-inductively coupled argon plasma mass spectrometry (ICP MS). Urine contained arsenobetaine (AsB, 1.0%), arsenite (iAs III , 11.3), arsenate (iAs V , 10.1), monomethylarsonous acid (MMA III , 6.6), monomethylarsonic acid (MMA V , 10.5), dimethylarsinous acid (DMA III , 13.0), and dimethylarsinic acid (DMA V , 47.5); fingernail contained iAs III (62.4%), iAs V (20.2), MMA V (5.7), DMA III (8.9), and DMA V (2.8); hair contained iAs III (58.9%), iAs V (34.8), MMA V (2.9), and DMA V (3.4); RBCs contained AsB (22.5%) and DMA V (77.5); and blood plasma contained AsB (16.7%), iAs III (21.1), MMA V (27.1), and DMA V (35.1). MMA III , DMA III , and iAs V were not found in any plasma and RBCs samples, but urine contained all of them. Arsenic in urine, fingernails, and hair are positively correlated with water As, suggesting that any of these measurements could be considered as a biomarker to As exposure. Status of urine and exogenous contamination of hair urgently need speciation of As in these samples, but speciation of As in nail is related to its total As (tAs) concentration. Therefore, total As concentrations of nails could be considered as biomarker to As exposure in the endemic areas

  3. Speciation needs in relation with environmental and biological purposes

    International Nuclear Information System (INIS)

    Moulin, V.; Ansoborlo, E.; Bion, L.; Doizi, D.; Moulin, C.; Cote, G.; Madic, C.; Van Der Lee, J.

    2004-01-01

    Radionuclides can occur in the environment either through chronic releases of nuclear facilities, or due to incidents or accidents. In order to study their behaviour in the environment (migration, retention, transfer, and in human organisms (metabolism, retention, excretion), it is of prime importance to know their solution chemistry, and more particularly thermodynamic constants, which will allow to determine their speciation. In fact, speciation governs the migration, the bioavailability and the toxicity of elements. Moreover, this knowledge is also of great interest for decorporation or decontamination purposes. In this framework, a CEA working group on speciation has been created in order to share data both on thermodynamic constants and on speciation analytical methods, interesting chemists, environmentalists and biologists. It has been focused, in a first time, on actinides, namely Th, U, Pu, Am, Np, taking into account their most important oxidation states occurring in environmental or biological environments: Th(IV), U(IV, VI), Pu(III, IV, VI), Am(III), Np(IV, V). A particular attention was devoted to the choice of ligands (inorganic and organic) for being the most representative of environmental and biological media. The thermodynamic database used is BASSIST for Base Applied to Speciation in Solution and at Interfaces and Solubility (developed by CEA), in interaction with the code JCHESS. Different examples will be then presented on the selection of data (thermodynamic constants, ligands of interest) through benchmark exercises (case of U(VI), Am(III), Pu(IV)) which will show the lacks or weakness of knowledge. Speciation diagrams will support these discussions. Moreover, analytical methods to determine thermodynamic constants or direct speciation will also be presented and discussed. (author)

  4. Potential application of SERS for arsenic speciation in biological matrices.

    Science.gov (United States)

    Yang, Mingwei; Matulis, Shannon; Boise, Lawrence H; McGoron, Anthony J; Cai, Yong

    2017-08-01

    Speciation of arsenic is usually carried out using chromatography-based methods coupled with spectroscopic determination; however, the inevitable procedures involving sample preparation and separation could potentially alter the integrity of the arsenic metabolites present in biological samples. Surface-enhanced Raman spectroscopy (SERS) could be a promising alternative for providing a reliable arsenic analysis under the influence of a cellular matrix. A method for arsenic speciation using SERS in cellular matrix was developed in this study and four arsenicals were selected, including arsenite (As III ), arsenate (As V ), monomethylarsonic acid (MMA V ) and dimethylarsinic acid (DMA V ). Silver nanoparticles in the form of colliodal suspension with different surface charges, i.e., coated with citrate (AgNPs-Citrate) and spermine (AgNPs-Spermine) were employed as SERS substrates. Adsorption of arsenicals on nanoparticles in colloidal suspensions and the cellular matrix and the pH, size, and zeta potential of the colloidal suspensions were investigated for a better understanding of the SERS signal response of arsenicals in the colloidal suspensions or under the influence of cellular matrix. Arsenicals showed substantially different SERS responses in the two colloidal suspensions, mainly because of the distinct difference in the interaction between the arsenicals and the nanoparticles. Arsenic speciation in cell lysate could be successfully carried out in AgNPs-Spermine suspension, while AgNPs-Citrate could not yield significant SERS signals under the experimental conditions. This study proved that AgNPs-Spermine colloidal suspension could be a promising SERS substrate for studying arsenic metabolism in a biological matrix, reducing the bias caused by traditional techniques that involve sample extraction and pretreatment.

  5. Arsenic in the aquatic environment - speciation and biological effects

    Energy Technology Data Exchange (ETDEWEB)

    Landner, L [Swedish Environmental Research Group (MFG)

    1998-03-01

    The present report is a contribution to EC Commission`s undertaking to review existing EC provisions on the substances for which Sweden has been granted transitional provisions. The provisions imply that Sweden may maintain more stringent regulations on four substances until the end of 1998. The present report deals with speciation and biological effects of arsenic in three types of aquatic environments - marine water, estuarine or brackish water and freshwater. The similarity between arsenate and phosphate and the interference in phosphorylation reactions is discussed. It is clear that in Scandinavian inland waters the concentration of phosphorous is on average lower than in most inland waters in continental Europe. However, in most inland waters phosphorus is the limiting factor for phytoplankton development and eutrophication, which means that there is a clear risk for detrimental effects in the great majority of inland waters, also eutrophic waters 167 refs, 27 figs, 12 tabs. Exemption Substances Project (Directive 89/677/EEC)

  6. Thermodynamics proposes, kinetics decides, speciation dares: speciation of actinides in biological media

    International Nuclear Information System (INIS)

    Ansoborlo, E.

    2005-06-01

    After having recalled the content and purpose of his research thesis, the author proposes a detailed overview of the research works he performed thereafter in the field of the speciation of actinides at the level of the organism entry gates and in target tissues. These works therefore concern four important areas of research in radioprotection: bio-kinetic, toxicology, decorporation, and dosimetry studies. The author outlines how speciation studies can be useful for these different areas, and to better understand and describe, and therefore foresee, the biokinetics and toxicity of radionuclides

  7. Analytical methodologies for aluminium speciation in environmental and biological samples--a review.

    Science.gov (United States)

    Bi, S P; Yang, X D; Zhang, F P; Wang, X L; Zou, G W

    2001-08-01

    It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited.

  8. Assessment of uranium and selenium speciation in human and bacterial biological models to probe changes in their structural environment

    Energy Technology Data Exchange (ETDEWEB)

    Avoscan, L.; Milgram, S.; Untereiner, G.; Collins, R.; Khodja, H.; Carriere, M.; Gouget, B. [Lab. Pierre Sue, CEA-CNRS UMR 9956, CEA/Saclay, Gif-sur-Yvette (France); Coves, J. [Inst. de Biologie Structurale - J.-P. Ebel, Lab. des Proteines Membranaires, Grenoble (France); Hazemann, J.L. [Lab. de Geophysique Interne et Tectonopbysique, UMR CNRS/Univ. Joseph Fourier, Saint-Martin-D' Heres (France)

    2009-07-01

    This study illustrates the potential of physicochemical techniques to speciate uranium (U) and selenium (Se) in biological samples. Speciation, defined he0re as the study of structural environment, of both toxic elements, was characterized at several levels in biological media and directly in human cells or bacteria once the metal(loid)s were internalized. External speciation that is extracellular speciation in culture media was predicted by thermodynamic equilibrium computer modelling using the JChess software and validated by spectroscopic measurements (XANES and EXAFS). Internal speciation that is intracellular speciation in eukaryotic and prokaryotic cells was studied in vitro with a soil bacterium Cupriavidus metallidurans CH34 and ROS 17/2.8 osteoblasts, human cells responsible for bone formation. XANES, EXAFS, HPLC-ICP-MS and SDS-PAGE coupled to particle induced X-ray emission (PIXE) permitted the identification and quantification of complexes formed with organic or inorganic molecules and/or larger proteins. (orig.)

  9. Assessment of uranium and selenium speciation in human and bacterial biological models to probe changes in their structural environment

    International Nuclear Information System (INIS)

    Avoscan, L.; Milgram, S.; Untereiner, G.; Collins, R.; Khodja, H.; Carriere, M.; Gouget, B.; Coves, J.; Hazemann, J.L.

    2009-01-01

    This study illustrates the potential of physicochemical techniques to speciate uranium (U) and selenium (Se) in biological samples. Speciation, defined he0re as the study of structural environment, of both toxic elements, was characterized at several levels in biological media and directly in human cells or bacteria once the metal(loid)s were internalized. External speciation that is extracellular speciation in culture media was predicted by thermodynamic equilibrium computer modelling using the JChess software and validated by spectroscopic measurements (XANES and EXAFS). Internal speciation that is intracellular speciation in eukaryotic and prokaryotic cells was studied in vitro with a soil bacterium Cupriavidus metallidurans CH34 and ROS 17/2.8 osteoblasts, human cells responsible for bone formation. XANES, EXAFS, HPLC-ICP-MS and SDS-PAGE coupled to particle induced X-ray emission (PIXE) permitted the identification and quantification of complexes formed with organic or inorganic molecules and/or larger proteins. (orig.)

  10. ISSEBETS 2009. 7. International Symposium on Speciation of Elements in Biological, Environmental and Toxicological Sciences

    International Nuclear Information System (INIS)

    2009-01-01

    The 7th ISSEBETS was held in August 2009 in city of Eger, Hungary. The main topics were: speciation of essential and toxic elements in food, in traditional drugs, designing functional foods through applied speciation, metallomics and metalloproteomics, metal species in health and disease, cycling of elemental species in the environment, speciation related regulations and legislation, metal environmental, bioremediation, quality assurance of speciation analysis. (S.I.)

  11. Liquid membrane extraction techniques for trace metal analysis and speciation in environmental and biological matrices

    Energy Technology Data Exchange (ETDEWEB)

    Ndungu, Kuria

    1999-04-01

    In this thesis, liquid-membrane-based methods for the analysis of trace metal species in samples of environmental and biological origin were developed. By incorporating extracting reagents in the membrane liquid, trace metal ions were selectively separated from humic-rich natural waters and urine samples, prior to their determination using various instrumental techniques. The extractions were performed in closed flow systems thus allowing easy automation of both the sample clean-up and enrichment. An acidic organophosphorus reagent (DEHPA) and a basic tetraalkylammonium reagent (Aliquat-336) were used as extractants in the membrane liquid to selectively extract and enrich cationic and anionic metal species respectively. A speciation method for chromium species was developed that allowed the determination of cationic Cr(III) species and anionic CR(VI) species in natural water samples without the need of a chromatographic separation step prior to their detection. SLM was also coupled on-line to potentiometric stripping analysis providing a fast and sensitive method for analysis of Pb in urine samples. A microporous membrane liquid-liquid extraction (MMLLE) method was developed for the determination of organotin compounds in natural waters that reduced the number of manual steps involved in the LLE of organotin compounds prior to their CC separation. Clean extracts obtained after running unfiltered humic-rich river water samples through the MMLLE flow system allowed selective determination of all the organotin compounds in a single run using GC-MS in the selected ion monitoring mode (SIM) 171 refs, 9 figs, 4 tabs

  12. Study of radionuclides speciation with biological molecules of interest by spectrometric techniques

    International Nuclear Information System (INIS)

    Lourenco, V.

    2007-07-01

    Mechanisms of complexation and accumulation of the radionuclides at the cellular and molecular level are complex and poorly known because the studies on these subjects are scarce. Within the framework of this thesis, we studied the interactions of europium (analogue of trivalent actinides) and uranium (VI) (actinide) with biological molecules of interest: phyto-chelatins. Their role is to protect cells against intrusions from nonessential heavy metals (thus toxic). These proteins are likely to be implied in the mechanisms of sequestration of radionuclides in living organisms. However, their structure is complex, this is why, in order to better understand their reactivity, we extended our studies to lower entities which constitute them (amino acids and glutathione). We determined solution speciation (stoichiometry, structure) as well as the complexing constants associated with the formation of these species. These studies were undertaken by Time Resolved Laser induced Fluorescence (TRLIF), Electro-Spray Mass Spectrometry (ES-MS), Nuclear Magnetic Resonance (NMR), Fourier Transform Infra-Rouge spectroscopy (FTIR) and Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS). The determination of the complexation constants enabled us to conclude that the complexing capacity of these molecules with respect to radionuclides was moderate (log 10 K 1 < 3, pH 3 or 6), the formed species are mononuclear with only one ligand molecule (1:1). The interaction is performed via oxygenated (hard) groups. The direct complexation of europium with phyto-chelatins at acidic pH was studied jointly by TRLIF and ES-MS. The complexing capacity of these molecules is much higher than that of GSH from which they result. In addition to studies undertaken on synthetic solutions reproducing the 'biological' conditions (pH close to neutrality, ionic strength 0.1 mol/L, etc), tests of cellular contamination were realized. The quantification of integrated europium showed that those are able to

  13. Study of radionuclides speciation with biological molecules of interest by spectrometric techniques

    International Nuclear Information System (INIS)

    Lourenco, V.

    2007-07-01

    Mechanisms of complexation and accumulation of the radionuclides at the cellular and molecular level are complex and poorly known because the studies on these subjects are scarce. Within the framework of this thesis, we studied the interactions of these cations with biological molecules of interest. We chose to focus on an actinide: uranium (VI) as well as europium as an analogue of trivalent actinides. The selected biological molecules are the phyto-chelatins: their role is to protect cells against intrusions from nonessential heavy metals (thus toxic). These proteins are likely to be implied in the mechanisms of sequestration of radionuclides in living organisms. However, their structure is complex, this is why, in order to better include/understand their reactivity, we extended our studies to lower entities which constitute them (amino acid: glycine, glutamic acid and cysteine; polypeptides: glutathione reduced and oxidized forms). In particular, we determined solution speciation (stoichiometry, structure) as well as the complexing constants associated with the formation with these species. These studies were undertaken by Time Resolved Laser induced Fluorescence (TRLIF), Electro-Spray-Mass Spectrometry (ES-MS), Nuclear Magnetic Resonance (NMR), Fourier Transform Infra-Rouge spectroscopy (FTIR) and Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS).The determination of the complexation constants enabled us to conclude that the complexing capacity of these molecules with respect to radionuclides was moderate (log 10 K 1 ≤ 3, pH 3 or 6), the formed species are mononuclear with only one ligand molecule (1:1). The interaction is performed via oxygenated (hard) groups. The direct complexation of europium with phyto-chelatins at acidic pH was studied jointly by TRLIF and ES-MS. The complexing capacity of these molecules is much higher than that of GSH from which they result. The interaction of europium with metallothioneins is, on the contrary, lower than

  14. Speciation of trace elements in biological samples by nuclear analytical and related techniques coupled with chemical and biochemical separation

    International Nuclear Information System (INIS)

    Chen, C.Y.; Gao, Y.X.; Li, B.; Yu, H.W.; Li, Y.F.; Sun, J.; Chai, Z.F.

    2005-01-01

    In the past, most analytical problems relating to biological systems were addressed by measuring the total concentrations of elements. Now there is increasing interest of the importance of their chemical forms, in which an element is present in biological systems, e.g., the oxidation state, the binding state with macromolecules, or even the molecular structure. The biological effects of chromium, which is classified as an essential nutrient, are dependent upon its oxidation. state. In general, trivalent chromium is biochemically active, whereas hexavalent chromium is considered to be toxic. Mercury is one of serious environmental persistent pollutants. However, organic forms of mercury are known to possess much higher toxicity than inorganic mercury. Therefore, information on speciation is critically required in order to better understanding of their bioavailability, metabolism, transformation, and toxicity in vivo. Recently, chemical speciation of selenium, mercury, copper, zinc, iron, and so on, has been investigated by INAA, ICP-MS, XRF, EXAFS and related techniques combined with chemical and biochemical separation (extraction, chromatography, gel electrophoresis, etc.). INAA, XRF, and ICP-MS have superior advantages in aspect of multielemental analysis with high accuracy and sensitivity, which render the possibility of analyzing various elements of interest simultaneously. These offline or online techniques have been flexibly applied to different biological matrixes, such as human hair, serum, urine, various tissues and organs in our researches. In addition, EXAFS provides structural information about the moiety of metal centers up to a distance of approximately 4-5 Anstrom. For instance, hepatocellular carcinoma (HCC) is one of the most common cancers worldwide. Imbalance of elements, such as Se, Zn, Fe, Cu, Cd, Ca, etc., has been found in the whole blood or serum of patients with HCC. We found that the profiles of Se, Cd, Fe, Zn and Cu-containing proteins

  15. A review on speciation of iodine-129 in the environmental and biological samples

    Energy Technology Data Exchange (ETDEWEB)

    Hou Xiaolin [Riso National Laboratory for Sustainable Energy, NUK-202, Technical University of Denmark, DK-4000 Roskilde (Denmark)], E-mail: xiaolin.hou@risoe.dk; Hansen, Violeta [Riso National Laboratory for Sustainable Energy, NUK-202, Technical University of Denmark, DK-4000 Roskilde (Denmark); Aldahan, Ala [Department of Earth Science, Uppsala University, SE-758 36 Uppsala (Sweden); Possnert, Goeran [Tandem Laboratory, Uppsala University, SE-751 21 Uppsala (Sweden); Lind, Ole Christian [Norwegian University of Life Science, N-1432, As (Norway); Lujaniene, Galina [Institute of Physics, Savanoriu 231, LT-0230 Vilnius (Lithuania)

    2009-01-26

    As a long-lived beta-emitting radioisotope of iodine, {sup 129}I is produced both naturally and as a result of human nuclear activities. At present time, the main part of {sup 129}I in the environment originates from the human nuclear activity, especially the releases from the spent nuclear fuel reprocessing plants, the {sup 129}I/{sup 127}I ratios have being reached to values of 10{sup -10} to 10{sup -4} in the environment from 10{sup -12} in the pre-nuclear era. In this article, we review the occurrence, sources, inventory, and concentration level of {sup 129}I in environment and the method for speciation analysis of {sup 129}I in the environment. Measurement techniques for the determination of {sup 129}I are presented and compared. An overview of applications of {sup 129}I speciation in various scientific disciplines such as radiation protection, waste depository, and environmental sciences is given. In addition, the bioavailability and radiation toxicity (dose to thyroid) of {sup 129}I are discussed.

  16. Assessment and evaluation of speciation tools for the study of uranium (6) circulating biological species

    International Nuclear Information System (INIS)

    Scapolan, St.

    1998-01-01

    The aim of this work is the development of tools allowing the study of uranium VI speciation in inorganic and organic environments, and in particular in the blood environment. The characterization of the different complexed forms of the uranyl ion has been improved by combining two techniques: the time resolution laser spectro-fluorimetry (TRLS) and the capillary electrophoresis (CE). CE is a developing separative analytical technique with a strong resolution. Therefore, the following studies have been carried out: the analysis of the speciation of hydroxo complexes of the uranyl ion by indirect UV detection, with the qualitative identification of the (UO 2 ) 2 (OH) 2 2+ and (UO 2 ) 3 (OH) 5 + complexes; the application of the iso-electrical focussing mode in order to show the uranium-transferrin complexing; the evaluation of the electrophoretic mobility of UO 2 2+ and the interactions with the phosphate, hydroxo-isobutyric acid (HIBA) and citrate ligands; and the study of the U(VI)-blood serum system with the separation of the different seric proteins and the influence of U(VI) on electrophoretic profiles. two points are important to consider in the development of the system: the coupling with an on-line detector (mass spectrometer, counter, laser) and the surface grafting of the capillaries used. The TRLS is a system used in geology, in the Purex process chemistry, in medical and environmental control, and in nuclear wastes management. After having analyzed the influence of different ligands (citrate, phosphate, carbonate, transferrin) in the fluorescence spectra of uranium (VI), the complexing conditional constant (K) of the U(VI)-transferrin system has been evaluated for the first time using a mathematical model and the titration. A study performed on blood plasma has permitted to show a U(VI)-phosphates complexing and finally, three phosphate complexes UO 2 H 2 PO 4 + , UO 2 HPO 4 and UO 2 PO 4 + have been characterized both spectrally and temporarily. (J.S.)

  17. The Investigation of Unexpected Arsenic Compounds Observed in Routine Biological Monitoring Urinary Speciation Analysis

    Directory of Open Access Journals (Sweden)

    Elizabeth Leese

    2017-05-01

    Full Text Available This study investigates the identity of two unexpected arsenic species found separately in a number of urine samples sent to the Health and Safety Executive’s Health and Safety Laboratory for arsenic speciation (arsenobetaine, AB; arsenite, As3+; arsenate, As5+; monomethylarsonic acid, MMA5+; and dimethylarsinic acid, DMA5+. Micro liquid chromatography coupled to inductively coupled plasma mass spectrometry (µLC-ICP-MS and electrospray time of flight tandem mass spectrometry (ESI-QqTOF-MS/MS were used to identify the two arsenic peaks by comparison to several characterized arsenicals: arsenocholine, AC; trimethyl arsine oxide, TMAO; dimethylarsenoacetate, DMAA; dimethylarsenoethanol, DMAE; thio-dimethylarsinate, thio-DMA; thio-dimethylarsenoacetate, thio-DMAA and thio-dimethylarsenoethanol, thio-DMAE. The results from both the ICP-MS and ESI-QqTOF-MS/MS investigations indicate that the unexpected arsenic species termed peak 1 was thio-DMA. While the unexpected arsenic species termed peak 2 has yet to be identified, this investigation shows that it was not AC, TMAO, DMAA, DMAE, thio-DMA, thio-DMAA or thio-DMAE. This study demonstrates the incidence of unexpected arsenic species in both routine and non-routine urine samples from both workers and hospital patients.

  18. Development and application of an ultratrace method for speciation of organotin compounds in cryogenically archived and homogenized biological materials

    Energy Technology Data Exchange (ETDEWEB)

    Point, David; Davis, W.C.; Christopher, Steven J.; Ellisor, Michael B.; Pugh, Rebecca S.; Becker, Paul R. [Hollings Marine Laboratory, National Institute of Standards and Technology, Analytical Chemistry Division, Charleston, SC (United States); Donard, Olivier F.X. [Laboratoire de Chimie Analytique BioInorganique et Environnement UMR 5034 du CNRS, Pau (France); Porter, Barbara J.; Wise, Stephen A. [National Institute of Standards and Technology, Analytical Chemistry Division, Gaithersburg, MD (United States)

    2007-04-15

    An accurate, ultra-sensitive and robust method for speciation of mono, di, and tributyltin (MBT, DBT, and TBT) by speciated isotope-dilution gas chromatography-inductively coupled plasma-mass spectrometry (SID-GC-ICPMS) has been developed for quantification of butyltin concentrations in cryogenic biological materials maintained in an uninterrupted cryo-chain from storage conditions through homogenization and bottling. The method significantly reduces the detection limits, to the low pg g{sup -1} level (as Sn), and was validated by using the European reference material (ERM) CE477, mussel tissue, produced by the Institute for Reference Materials and Measurements. It was applied to three different cryogenic biological materials - a fresh-frozen mussel tissue (SRM 1974b) together with complex materials, a protein-rich material (whale liver control material, QC03LH03), and a lipid-rich material (whale blubber, SRM 1945) containing up to 72% lipids. The commutability between frozen and freeze-dried materials with regard to spike equilibration/interaction, extraction efficiency, and the absence of detectable transformations was carefully investigated by applying complementary methods and by varying extraction conditions and spiking strategies. The inter-method results enabled assignment of reference concentrations of butyltins in cryogenic SRMs and control materials for the first time. The reference concentrations of MBT, DBT, and TBT in SRM 1974b were 0.92 {+-} 0.06, 2.7 {+-} 0.4, and 6.58 {+-} 0.19 ng g{sup -1} as Sn (wet-mass), respectively; in SRM 1945 they were 0.38 {+-} 0.06, 1.19 {+-} 0.26, and 3.55 {+-} 0.44 ng g{sup -1}, respectively, as Sn (wet-mass). In QC03LH03, DBT and TBT concentrations were 30.0 {+-} 2.7 and 2.26 {+-} 0.38 ng g{sup -1} as Sn (wet-mass). The concentration range of butyltins in these materials is one to three orders of magnitude lower than in ERM CE477. This study demonstrated that cryogenically processed and stored biological materials are

  19. Arsenic speciation in biological environmental samples of aquatic ecosystems by using HPLC-ICP-MS; Speciation von Arsen in biologischen Umweltproben aus aquatischen Oekosystemen mittels HPLC-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Falk, K.

    1999-09-01

    The physicochemical forms of arsenic (arsenic species) which are present in the environment vary significantly with respect to toxicity, bioavailability, stability and transport behaviour. Therefore, it is necessary for an assessment of the toxic potential to humans and the environment to investigate not only the total arsenic concentrations but also to differentiate the single species. By that the knowledge about ecological correlations and pathways will be increased. The present thesis reports the results of a Ph.D. study on the development and optimisation of analytical methods for arsenic speciation and their application to biological samples from different aquatic ecosystems in Germany. The method development included separation of 12 naturally occurring arsenic species by high-performance liquid chromatography (HPLC) followed by an arsenic selective detection by inductively coupled plasma-mass spectrometry (ICP-MS). The arsenic species As (III), As (V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AB), arsenocholine (AC), trimethylarsine oxid (TMAO) and tetramethylarsonium (Tetra) were separated with ion-exchange chromatography, whereas reversed-phase chromatography was used for the separation of four arsenosugars. Because of the partly low arsenic concentration in biological samples a very good detection power was required. Therefore, an HPLC-ICP-MS system was tested with different nebulizers. Using the high efficiency nebulizer HHPN (Hydraulic High Pressure Nebulizer), detection limits in the low pg-range could be achieved. The developed analytical methods were applied to arsenic speciation in four marine matrices, which are representative of different trophic levels in the food chain. All samples originated from an ecosystem in the North Sea.

  20. Ultra-Sensitive Elemental Analysis Using Plasmas 5.Speciation of Arsenic Compounds in Biological Samples by High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry System

    Science.gov (United States)

    Kaise, Toshikazu

    Arsenic originating from the lithosphere is widely distributed in the environment. Many arsenicals in the environment are in organic and methylated species. These arsenic compounds in drinking water or food products of marine origin are absorbed in human digestive tracts, metabolized in the human body, and excreted viatheurine. Because arsenic shows varying biological a spects depending on its chemical species, the biological characteristics of arsenic must be determined. It is thought that some metabolic pathways for arsenic and some arsenic circulation exist in aqueous ecosystems. In this paper, the current status of the speciation analysis of arsenic by HPLC/ICP-MS (High Performance Liquid Chromatography-Inductively Coupled Plasma Mass spectrometry) in environmental and biological samples is summarized using recent data.

  1. Study of radionuclides speciation with biological molecules of interest by spectrometric techniques; Etude de la speciation des radionucleides avec les molecules d'interet biologique par approche spectrometrique

    Energy Technology Data Exchange (ETDEWEB)

    Lourenco, V

    2007-07-15

    Mechanisms of complexation and accumulation of the radionuclides at the cellular and molecular level are complex and poorly known because the studies on these subjects are scarce. Within the framework of this thesis, we studied the interactions of these cations with biological molecules of interest. We chose to focus on an actinide: uranium (VI) as well as europium as an analogue of trivalent actinides. The selected biological molecules are the phyto-chelatins: their role is to protect cells against intrusions from nonessential heavy metals (thus toxic). These proteins are likely to be implied in the mechanisms of sequestration of radionuclides in living organisms. However, their structure is complex, this is why, in order to better include/understand their reactivity, we extended our studies to lower entities which constitute them (amino acid: glycine, glutamic acid and cysteine; polypeptides: glutathione reduced and oxidized forms). In particular, we determined solution speciation (stoichiometry, structure) as well as the complexing constants associated with the formation with these species. These studies were undertaken by Time Resolved Laser induced Fluorescence (TRLIF), Electro-Spray-Mass Spectrometry (ES-MS), Nuclear Magnetic Resonance (NMR), Fourier Transform Infra-Rouge spectroscopy (FTIR) and Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS).The determination of the complexation constants enabled us to conclude that the complexing capacity of these molecules with respect to radionuclides was moderate (log{sub 10}K{sub 1} {<=} 3, pH 3 or 6), the formed species are mononuclear with only one ligand molecule (1:1). The interaction is performed via oxygenated (hard) groups. The direct complexation of europium with phyto-chelatins at acidic pH was studied jointly by TRLIF and ES-MS. The complexing capacity of these molecules is much higher than that of GSH from which they result. The interaction of europium with metallothioneins is, on the contrary

  2. Method development for speciation analysis of nanoparticle and ionic forms of gold in biological samples by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Malejko, Julita; Świerżewska, Natalia; Bajguz, Andrzej; Godlewska-Żyłkiewicz, Beata

    2018-04-01

    A new method based on coupling high performance liquid chromatography (HPLC) to inductively coupled plasma mass spectrometry (ICP MS) has been developed for the speciation analysis of gold nanoparticles (AuNPs) and dissolved gold species (Au(III)) in biological samples. The column type, the composition and the flow rate of the mobile phase were carefully investigated in order to optimize the separation conditions. The usefulness of two polymeric reversed phase columns (PLRP-S with 100 nm and 400 nm pore size) to separate gold species were investigated for the first time. Under the optimal conditions (PLRP-S400 column, 10 mmol L-1 SDS and 5% methanol as the mobile phase, 0.5 mL min-1 flow rate), detection limits of 2.2 ng L-1 for Au(III), 2.8 ng L-1 for 10 nm AuNPs and 3.7 ng L-1 for 40 nm AuNPs were achieved. The accuracy of the method was proved by analysis of reference material RM 8011 (NIST) of gold nanoparticles of nominal diameter of 10 nm. The HPLC-ICP MS method has been successfully applied to the detection and size characterization of gold species in lysates of green algae Acutodesmus obliquus, typical representative of phytoplankton flora, incubated with 10 nm AuNPs or Au(III).

  3. Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

    Science.gov (United States)

    This paper describes an automated system for the oxidation state specific speciation of inorganic and methylated arsenicals by selective hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer. The corresponding arsines are ge...

  4. X exceptionalism in Caenorhabditis speciation.

    Science.gov (United States)

    Cutter, Asher D

    2017-11-13

    Speciation genetics research in diverse organisms shows the X-chromosome to be exceptional in how it contributes to "rules" of speciation. Until recently, however, the nematode phylum has been nearly silent on this issue, despite the model organism Caenorhabditis elegans having touched most other topics in biology. Studies of speciation with Caenorhabditis accelerated with the recent discovery of species pairs showing partial interfertility. The resulting genetic analyses of reproductive isolation in nematodes demonstrate key roles for the X-chromosome in hybrid male sterility and inviability, opening up new understanding of the genetic causes of Haldane's rule, Darwin's corollary to Haldane's rule, and enabling tests of the large-X effect hypothesis. Studies to date implicate improper chromatin regulation of the X-chromosome by small RNA pathways as integral to hybrid male dysfunction. Sexual transitions in reproductive mode to self-fertilizing hermaphroditism inject distinctive molecular evolutionary features into the speciation process for some species. Caenorhabditis also provides unique opportunities for analysis in a system with XO sex determination that lacks a Y-chromosome, sex chromosome-dependent sperm competition differences and mechanisms of gametic isolation, exceptional accessibility to the development process and rapid experimental evolution. As genetic analysis of reproductive isolation matures with investigation of multiple pairs of Caenorhabditis species and new species discovery, nematodes will provide a powerful complement to more established study organisms for deciphering the genetic basis of and rules to speciation. © 2017 John Wiley & Sons Ltd.

  5. Advances in Ecological Speciation: an integrative approach.

    Science.gov (United States)

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

    2014-02-01

    The role of natural selection in promoting reproductive isolation has received substantial renewed interest within the last two decades. As a consequence, the study of ecological speciation has become an extremely productive research area in modern evolutionary biology. Recent innovations in sequencing technologies offer an unprecedented opportunity to study the mechanisms involved in ecological speciation. Genome scans provide significant insights but have some important limitations; efforts are needed to integrate them with other approaches to make full use of the sequencing data deluge. An international conference 'Advances in Ecological Speciation' organized by the University of Porto (Portugal) aimed to review current progress in ecological speciation. Using some of the examples presented at the conference, we highlight the benefits of integrating ecological and genomic data and discuss different mechanisms of parallel evolution. Finally, future avenues of research are suggested to advance our knowledge concerning the role of natural selection in the establishment of reproductive isolation during ecological speciation. © 2013 John Wiley & Sons Ltd.

  6. Island emergence/subsidence histories and their bearing upon biological speciation in the Galápagos

    Science.gov (United States)

    Orellana Rovirosa, F.

    2017-12-01

    In the context of plate motion reconstructions for the Nazca, Cocos and South American plates in relation with the Galápagos hotspot, it is found that the age-depth dependence of bathymetry, dynamic topography due to the Galápagos plume, crustal relaxation, and magmatic production allow for us to estimate the subsidence of islands and seamounts along the Carnegie Ridge. Our estimates are partially based on geodynamic theory (fluid mechanics and elasticity), but also on detailed bathymetric observations and analysis. For the Carnegie Ridge saddle, we estimate subsidence of about 2 km occurring during the past 13 Ma. Because the present-day depths of the region are in the range 2-2.5 km, this assessment shows that the deepest region of the present-day Carnegie Ridge may have been above sea level when it was closer to the active hotspot, therefore providing habitat for land species for a few (Carnegie Ridge on a spatio-temporal progression. A more sophisticated 3D numerical model including an asthenosphere and plume interacting with the overlying Nazca plate may provide an improved understanding of geological-biological co-evolution in the Galápagos-Carnegie Ridge.

  7. Speciation analysis of radionuclides

    International Nuclear Information System (INIS)

    Salbu, B.

    2010-01-01

    Full text: Naturally occurring and artificially produced radionuclides in the environment can be present in different physico-chemical forms (i. e. radionuclide species) varying in size (nominal molecular mass), charge properties and valence, oxidation state, structure and morphology, density, complexing ability etc. Low molecular mass (LMM) species are believed to be mobile and potentially bioavailable, while high molecular mass (HMM) species such as colloids, polymers, pseudocolloids and particles are considered inert. Due to time dependent transformation processes such as mobilization of radionuclide species from solid phases or interactions of mobile and reactive radionuclide species with components in soils and sediments, however, the original distribution of radionuclides deposited in ecosystems will change over time and influence the ecosystem behaviour. To assess the environmental impact from radionuclide contamination, information on radionuclide species deposited, interactions within affected ecosystems and the time-dependent distribution of radionuclide species influencing mobility and biological uptake is essential. The development of speciation techniques to characterize radionuclide species in waters, soils and sediments should therefore be essential for improving the prediction power of impact and risk assessment models. The present paper reviews fractionation techniques which should be utilised for radionuclide speciation purposes. (author)

  8. Bioaccumulation of selenium and induced biological effects in the filter feeding bivalve Corbicula fluminea: influence of ventilatory activity, selenium speciation and route of transfer

    International Nuclear Information System (INIS)

    Fournier, E.

    2005-10-01

    Selenium is an essential micro-nutrient for most of living organisms. However, toxic effects in several ecosystems have been reported in the literature. Toxicity comprehension is difficult due to the complexity of Se oxidation states in the environment. The aim of this thesis work was to acquire knowledge on the physiological and environmental factors involved in bioaccumulation and toxicity processes in the freshwater filter-feeding bivalve C. fluminea. The aims were: i) to define what the factors involved in Se bioaccumulation processes in the bivalve are, ii) to characterize Se bioaccumulation at different biological organisation levels, iii) to investigate Se toxic effects. First experiments, carried out for short term exposure duration (3 days), have permitted to underline the importance of Se chemical speciation in bioaccumulation processes in C. fluminea. It has been shown that the organic form, seleno-methionine, was much more bio-available than the inorganic forms, selenite and selenate. Moreover, the route of transfer was determinant in those processes. Inorganic forms have been better extracted by trophic route, whereas seleno-methionine has been better extracted by the direct route. In our experimental conditions, ventilation of the bivalve has not been a limiting factor for Se bioaccumulation by the direct route, whereas it has been for bioaccumulation by the trophic route. Ventilation has been largely modified by the presence of dissolved selenite and seleno-methionine. We have shown that the kinetics of seleno-methionine bioaccumulation are much more fast than those of selenite. Moreover, when introduced as SeMet, internalized Se appeared to be relatively remanent in soft tissues of C. fluminea in comparison with Se internalized when introduced as selenite. Subcellular and molecular distributions of these forms were very different. Finally, it has been shown that seleno-methionine and selenite could generate weak alterations of the anti

  9. What do we need to know about speciation?

    NARCIS (Netherlands)

    Butlin, Roger; Debelle, Allan; Kerth, Claudius; Snook, Rhonda R.; Beukeboom, Leo W.; Castillo Cajas, Ruth; Diao, Wenwen; Maan, Martine E.; Paolucci, Silvia; Weissing, Franz J.; van de Zande, Louis; Hoikkala, Anneli; Geuverink, Elzemiek; Jennings, Jackson; Kankare, Maaria; Knott, K. Emily; Tyukmaeva, Venera I.; Zoumadakis, Christos; Ritchie, Michael G.; Barker, Daniel; Immonen, Elina; Kirkpatrick, Mark; Noor, Mohamed; Macias Garcia, Constantino; Schmitt, Thomas; Schilthuizen, Menno

    Speciation has been a major focus of evolutionary biology research in recent years, with many important advances. However, some of the traditional organising principles of the subject area no longer provide a satisfactory framework, such as the classification of speciation mechanisms by geographical

  10. Biosensor for metal analysis and speciation

    Science.gov (United States)

    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.

  11. Arsenic speciation results

    Data.gov (United States)

    U.S. Environmental Protection Agency — Linear combination fitting results of synchrotron data to determine arsenic speciation in soil samples. This dataset is associated with the following publication:...

  12. Chemical Speciation - General Information

    Science.gov (United States)

    This page includes general information about the Chemical Speciation Network that is not covered on the main page. Commonly visited documents, including calendars, site lists, and historical files for the program are listed here

  13. Searching for speciation genes

    DEFF Research Database (Denmark)

    Holt, Benjamin George; Côté, Isabelle M; Emerson, Brent C

    2011-01-01

    Closely related species that show clear phenotypic divergence, but without obvious geographic barriers, can provide opportunities to study how diversification can occur when opportunities for allopatric speciation are limited. We examined genetic divergence in the coral reef fish genus Hypoplectrus...

  14. Speciation by Symbiosis: the Microbiome and Behavior.

    Science.gov (United States)

    Shropshire, J Dylan; Bordenstein, Seth R

    2016-03-31

    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. Copyright © 2016 Shropshire and Bordenstein.

  15. Uranium speciation in plants

    International Nuclear Information System (INIS)

    Guenther, A.; Bernhard, G.; Geipel, G.; Reich, T.; Rossberg, A.; Nitsche, H.

    2003-01-01

    Detailed knowledge of the nature of uranium complexes formed after the uptake by plants is an essential prerequisite to describe the migration behavior of uranium in the environment. This study focuses on the determination of uranium speciation after uptake of uranium by lupine plants. For the first time, time-resolved laser-induced fluorescence spectroscopy and X-ray absorption spectroscopy were used to determine the chemical speciation of uranium in plants. Differences were detected between the uranium speciation in the initial solution (hydroponic solution and pore water of soil) and inside the lupine plants. The oxidation state of uranium did not change and remained hexavalent after it was taken up by the lupine plants. The chemical speciation of uranium was identical in the roots, shoot axis, and leaves and was independent of the uranium speciation in the uptake solution. The results indicate that the uranium is predominantly bound as uranyl(VI) phosphate to the phosphoryl groups. Dandelions and lamb's lettuce showed uranium speciation identical to lupine plants. (orig.)

  16. Root uptake of uranium (6) in solution by a higher plant: speciation in hydroponic solution, bioavailability, micro-localisation and biological effects induced

    International Nuclear Information System (INIS)

    Laroche, L.

    2005-01-01

    Uranium exists naturally in the environment, usually present in trace quantities. In soil solution and oxic conditions, uranium is present in the +VI oxidation state and forms a large number of inorganic and organic complexes. The exposure medium, an artificial soil solution, was designed in such a way as to control the uranium species in solution. The geochemical speciation code JCHESS was used to calculate the uranium aqueous species concentration and to define the domains of interest, each of them characterized by a limited number of dominant U species. These domains were defined as follows: pH 4.9 with uranyl ions as dominant species, pH 5.8 with hydroxyl complexes and pH 7 where carbonates play a major role. For each pH, short-duration (5 hours of exposure) well-defined laboratory experiments were carried out with Phaseolus vulgaris as plant model. The effect of competitive ions such as Ca 2+ or the presence of ligands such as phosphate or citrate on root assimilation efficiency was explored. Results have shown that uranium transfer was not affected by the presence of calcium, phosphate or citrate (but was decreased of 60% with citrate (10 μM) at pH 5.8) in our experimental conditions. Moreover, observation in Transmission Electronic Microscopy (TEM), equipped with an EDAX probe, have shown that uranium was associated with granules rich in phosphorus and that there were some chloroplast anomalies. Finally, the presence of uranium affects root CEC by reducing it and stimulates root elongation at low uranium concentrations (100 nM, 400 nM and 2 μM at pHs 4.9, 5.8 and 7 respectively) and inhibits it at high uranium concentrations. (author)

  17. Speciation issues in food control - are we ready?

    International Nuclear Information System (INIS)

    Sloth, J.J.; Hedegaard, R.V.; Julshamn, K.; Trier, X.T.; Larsen, E.H.

    2009-01-01

    Full text: Our understanding of the mechanisms of biological activities and biotransformation of trace elements has improved during recent years with the help of chemical speciation studies. However, the most important practical application of elemental speciation is in the area of toxicology. Toxicological knowledge on the individual chemical elemental species should lead to more specific legislation of hazardous substances. Presently, European legislation concerning food safety is based on total element concentrations expressed as maximum limits. The lecture focuses on the present situation for speciation in food control and discusses the latest and expected future developments within this area. (author)

  18. Speciation of arsenic and mercury in feed: why and how?

    DEFF Research Database (Denmark)

    Hedegaard, Rikke Susanne Vingborg; Sloth, Jens Jørgen

    2011-01-01

    The understanding of the mechanisms of biological activities and biotransformation of trace elements such as arsenic and mercury has improved during recent years with the help of chemical speciation studies. However, the most important practical application of elemental speciation is in the area ...... in feed as well as initiatives for the establishment of standardized methods for determination of inorganic arsenic and methylmercury are presented.......The understanding of the mechanisms of biological activities and biotransformation of trace elements such as arsenic and mercury has improved during recent years with the help of chemical speciation studies. However, the most important practical application of elemental speciation is in the area...... of toxicology. Toxicological knowledge on the individual trace element species can lead to more specific legislation of hazardous substances found in feed. Examples here are arsenic, where the inorganic forms are the most toxic, and mercury, where the organic form methylmercury is more toxic than inorganic...

  19. Speciation and internal dosimetry: from chemical species to dosimetric models

    International Nuclear Information System (INIS)

    Paquet, F.; Frelon, S.; Cote, G.; Madic, C.

    2004-01-01

    Speciation studies refer to the distribution of species in a particular sample or matrix. These studies are necessary to improve the description, understanding and prediction of trace element kinetics and toxicity. In case of internal contamination with radionuclides, speciation studies could help to improve both the biokinetic and dosimetric models for radionuclides. There are different methods to approach the speciation of radionuclide in a biological system, depending on the degree of accuracy needed and the level of uncertainties accepted. Among them, computer modelling and experimental determination are complementary approaches. This paper describes what is known about speciation of actinides in blood, GI-tract, liver and skeleton and of their consequences in terms of internal dosimetry. The conclusion is that such studies provide very valuable data and should be targeted in the future on some specific tissues and biomolecules. (authors)

  20. The contribution of chemical speciation to internal dosimetry

    International Nuclear Information System (INIS)

    Paquet, F.; Frelon, S.; Cote, G.; Madic, C.

    2003-01-01

    Speciation studies refer to the distribution of species in a particular sample or matrix. These studies are necessary to improve the description, understanding and prediction of trace element kinetics and toxicity. In the case of internal contamination with radionuclides, speciation studies could help to improve both the biokinetic and dosimetric models for radionuclides. There are different methods to approach the speciation of radionuclides in a biological system, depending on the degree of accuracy needed and the level of uncertainties accepted. Among them, computer modelling and experimental determination are complementary approaches. This paper describes what is known about speciation of actinides in blood, GI tract, liver and skeleton and of their consequences in terms of internal dosimetry. The conclusion is that such studies provide very valuable data and should be targeted in the future on some specific tissues and biomolecules. (author)

  1. Volatile organo-selenium speciation in biological matter by solid phase microextraction-moderate temperature multicapillary gas chromatography with microwave induced plasma atomic emission spectrometry detection

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, C.; Sanz Landaluze, J.; Ximenez-Embun, P.; Madrid-Albarran, Y.; Camara, C

    2004-01-16

    Microwave induced plasma atomic emission spectrometry (MIP-AES) in combination with multicapillary (MC) gas chromatography could be proven to be useful for element specific detection of volatile species. Solid phase microextraction (SPME) was used for preconcentration and sample-matrix separation. The fiber desorption unit as well as the heating control for the MC column were in-house developed and multicapillary column was operated at moderate temperatures (30-100 deg. C). The method was optimized for organo-selenium species (dimethylselenide (DMSe), diethylselenide (DEtSe) and dimethyldiselenide (DMDSe)), using a chemometric approach. Stationary phases for the separation column were optimized using a conventional GC and contrasted with the results obtained with the MC. Application was focussed on selenium accumulating biological matter, such as lupine, yeast, Indian mustard and garlic. These samples were grown in hydroponic solution containing inorganic selenium (Na{sub 2}SeO{sub 3} and Na{sub 2}SeO{sub 4}). SPME sampling was carried out in fixed volume flow boxes in headspace above the living plants and in vials using treated samples. Results demonstrate inorganic selenium transformation into volatile organic species during metabolism. Separation is fast, a chromatogram can be obtained in less than 3 min and detection limits were at sub-ppb level for all investigated species. The system is independent from the use of a conventional gas chromatographic oven and can be used as a versatile alternative to highly cost intensive methods such as GC-ICP-MS.

  2. Trace element speciation in the environment

    International Nuclear Information System (INIS)

    Heumann, Klaus G.

    2001-01-01

    The production of methylated heavy metal species in the ocean was reviewed and shown to be correlated with biological parameters demonstrating them to be of biogenic origin. Methods for the determination of the species were discussed. The potential for the use of isotopic spiking either in 'species specific' or 'non-species specific' formats was identified as a valuable tool in the struggle for accuracy, specificity and precision in speciation analysis. The value of using a size exclusion chromatographic method in conjunction with non-species specific spiking IDMS was highlighted with an example illustrating the molecular mass fractions associated with halogenated species from a humic sample. Additional recommendations that the Agency might wish to consider when evaluating its potential role as a service to Member States engaged in speciation activities are also given

  3. The importance of element speciation in water analysis - a plea for further investigations

    International Nuclear Information System (INIS)

    Frimmel, F.H.; Gremm, T.

    1994-01-01

    Water analysis is dominated by parameters given in laws and recommendations concerning water quality. Speciation has been broadly neglected. This might be due to the difficulties in defining speciation and in determining species at low concentrations. This paper addresses the physical, chemical and biological approaches to speciation and gives examples for methods which are suited for species determination in aquatic systems. Metals and non-metallic elements are covered as well. It is obvious that speciation is a key for understanding the function of aquatic ecosystems and their technical utilization. (orig.)

  4. Differential survival between visual environments supports a role of divergent sensory drive in cichlid fish speciation

    NARCIS (Netherlands)

    Maan, Martine E.; Seehausen, Ole; Groothuis, Ton G. G.

    Identifying the selective forces that initiate ecological speciation is a major challenge in evolutionary biology. Sensory drive has been implicated in speciation in various taxa, largely based on phenotype-environment correlations and signatures of selection in sensory genes. Here, we present a

  5. Arsenic Speciation in Groundwater: Role of Thioanions

    Science.gov (United States)

    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...

  6. Bioaccumulation of selenium and induced biological effects in the filter feeding bivalve Corbicula fluminea: influence of ventilatory activity, selenium speciation and route of transfer; Bioaccumulation du selenium et effets biologiques induits chez le bivalve filtreur Corbicula fluminea: prise en compte de l'activite ventilatoire, de la speciation du selenium et de la voie de contamination

    Energy Technology Data Exchange (ETDEWEB)

    Fournier, E

    2005-10-15

    Selenium is an essential micro-nutrient for most of living organisms. However, toxic effects in several ecosystems have been reported in the literature. Toxicity comprehension is difficult due to the complexity of Se oxidation states in the environment. The aim of this thesis work was to acquire knowledge on the physiological and environmental factors involved in bioaccumulation and toxicity processes in the freshwater filter-feeding bivalve C. fluminea. The aims were: i) to define what the factors involved in Se bioaccumulation processes in the bivalve are, ii) to characterize Se bioaccumulation at different biological organisation levels, iii) to investigate Se toxic effects. First experiments, carried out for short term exposure duration (3 days), have permitted to underline the importance of Se chemical speciation in bioaccumulation processes in C. fluminea. It has been shown that the organic form, seleno-methionine, was much more bio-available than the inorganic forms, selenite and selenate. Moreover, the route of transfer was determinant in those processes. Inorganic forms have been better extracted by trophic route, whereas seleno-methionine has been better extracted by the direct route. In our experimental conditions, ventilation of the bivalve has not been a limiting factor for Se bioaccumulation by the direct route, whereas it has been for bioaccumulation by the trophic route. Ventilation has been largely modified by the presence of dissolved selenite and seleno-methionine. We have shown that the kinetics of seleno-methionine bioaccumulation are much more fast than those of selenite. Moreover, when introduced as SeMet, internalized Se appeared to be relatively remanent in soft tissues of C. fluminea in comparison with Se internalized when introduced as selenite. Subcellular and molecular distributions of these forms were very different. Finally, it has been shown that seleno-methionine and selenite could generate weak alterations of the anti

  7. Hitchhiking to speciation.

    Directory of Open Access Journals (Sweden)

    Daven C Presgraves

    Full Text Available The modern evolutionary synthesis codified the idea that species exist as distinct entities because intrinsic reproductive barriers prevent them from merging together. Understanding the origin of species therefore requires understanding the evolution and genetics of reproductive barriers between species. In most cases, speciation is an accident that happens as different populations adapt to different environments and, incidentally, come to differ in ways that render them reproductively incompatible. As with other reproductive barriers, the evolution and genetics of interspecific hybrid sterility and lethality were once also thought to evolve as pleiotripic side effects of adaptation. Recent work on the molecular genetics of speciation has raised an altogether different possibility-the genes that cause hybrid sterility and lethality often come to differ between species not because of adaptation to the external ecological environment but because of internal evolutionary arms races between selfish genetic elements and the genes of the host genome. Arguably one of the best examples supporting a role of ecological adaptation comes from a population of yellow monkey flowers, Mimulus guttatus, in Copperopolis, California, which recently evolved tolerance to soil contaminants from copper mines and simultaneously, as an incidental by-product, hybrid lethality in crosses with some off-mine populations. However, in new work, Wright and colleagues show that hybrid lethality is not a pleiotropic consequence of copper tolerance. Rather, the genetic factor causing hybrid lethality is tightly linked to copper tolerance and spread to fixation in Copperopolis by genetic hitchhiking.

  8. Something's Fishy in Paxton Lake: A Case on Speciation in Sticklebacks.

    Science.gov (United States)

    Sharp, Joan

    2002-01-01

    Introduces a case study on speciation and evolutionary mechanisms. Teaches science process skills as well as natural selection, biological species concepts, basic genetic terminology, and classification. Includes teaching notes and classroom management strategies. (Contains 14 references.) (YDS)

  9. Signals of speciation within Arabidopsis thaliana in comparison with its relatives

    NARCIS (Netherlands)

    Alcazar, R.; Pecinka, A.; Aarts, M.G.M.; Fransz, P.F.; Koornneef, M.

    2012-01-01

    The species within the now well-defined Arabidopsis genus provide biological materials suitable to investigate speciation and the development of reproductive isolation barriers between related species. Even within the model species A. thaliana, genetic differentiation between populations due to

  10. Investigating ecological speciation in non-model organisms

    DEFF Research Database (Denmark)

    Foote, Andrew David

    2012-01-01

    Background: Studies of ecological speciation tend to focus on a few model biological systems. In contrast, few studies on non-model organisms have been able to infer ecological speciation as the underlying mechanism of evolutionary divergence. Questions: What are the pitfalls in studying ecological...... speciation in non-model organisms that lead to this bias? What alternative approaches might redress the balance? Organism: Genetically differentiated types of the killer whale (Orcinus orca) exhibiting differences in prey preference, habitat use, morphology, and behaviour. Methods: Review of the literature...... on killer whale evolutionary ecology in search of any difficulty in demonstrating causal links between variation in phenotype, ecology, and reproductive isolation in this non-model organism. Results: At present, we do not have enough evidence to conclude that adaptive phenotype traits linked to ecological...

  11. Extensive range overlap between heliconiine sister species: evidence for sympatric speciation in butterflies?

    Science.gov (United States)

    Rosser, Neil; Kozak, Krzysztof M; Phillimore, Albert B; Mallet, James

    2015-06-30

    Sympatric speciation is today generally viewed as plausible, and some well-supported examples exist, but its relative contribution to biodiversity remains to be established. We here quantify geographic overlap of sister species of heliconiine butterflies, and use age-range correlations and spatial simulations of the geography of speciation to infer the frequency of sympatric speciation. We also test whether shifts in mimetic wing colour pattern, host plant use and climate niche play a role in speciation, and whether such shifts are associated with sympatry. Approximately a third of all heliconiine sister species pairs exhibit near complete range overlap, and analyses of the observed patterns of range overlap suggest that sympatric speciation contributes 32%-95% of speciation events. Müllerian mimicry colour patterns and host plant choice are highly labile traits that seem to be associated with speciation, but we find no association between shifts in these traits and range overlap. In contrast, climatic niches of sister species are more conserved. Unlike birds and mammals, sister species of heliconiines are often sympatric and our inferences using the most recent comparative methods suggest that sympatric speciation is common. However, if sister species spread rapidly into sympatry (e.g. due to their similar climatic niches), then assumptions underlying our methods would be violated. Furthermore, although we find some evidence for the role of ecology in speciation, ecological shifts did not show the associations with range overlap expected under sympatric speciation. We delimit species of heliconiines in three different ways, based on "strict and " "relaxed" biological species concepts (BSC), as well as on a surrogate for the widely-used "diagnostic" version of the phylogenetic species concept (PSC). We show that one reason why more sympatric speciation is inferred in heliconiines than in birds may be due to a different culture of species delimitation in the two

  12. CHURCH, Category, and Speciation

    Directory of Open Access Journals (Sweden)

    Rinderknecht Jakob Karl

    2018-01-01

    Full Text Available The Roman Catholic definition of “church”, especially as applied to groups of Protestant Christians, creates a number of well-known difficulties. The similarly complex category, “species,” provides a model for applying this term so as to neither lose the centrality of certain examples nor draw a hard boundary to rule out border cases. In this way, it can help us to more adequately apply the complex ecclesiology of the Second Vatican Council. This article draws parallels between the understanding of speciation and categorization and the definition of Church since the council. In doing so, it applies the work of cognitive linguists, including George Lakoff, Zoltan Kovecses, Giles Fauconnier and Mark Turner on categorization. We tend to think of categories as containers into which we sort objects according to essential criteria. However, categories are actually built inductively by making associations between objects. This means that natural categories, including species, are more porous than we assume, but nevertheless bear real meaning about the natural world. Taxonomists dispute the border between “zebras” and “wild asses,” but this distinction arises out of genetic and evolutionary reality; it is not merely arbitrary. Genetic descriptions of species has also led recently to the conviction that there are four species of giraffe, not one. This engagement will ground a vantage point from which the Council‘s complex ecclesiology can be more easily described so as to authentically integrate its noncompetitive vision vis-a-vis other Christians with its sense of the unique place held by Catholic Church.

  13. Cancer: beyond speciation.

    Science.gov (United States)

    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

  14. CONCAWE effluent speciation project

    Energy Technology Data Exchange (ETDEWEB)

    Leonards, P.; Comber, M.; Forbes, S.; Whale, G.; Den Haan, K.

    2010-09-15

    In preparation for the implementation of the EU REACH regulation, a project was undertaken to transfer the high-resolution analytical method for determining hydrocarbon blocks in petroleum products by comprehensive two-dimensional gas chromatography (GCxGC) to a laboratory external to the petroleum industry (Institute for Environmental Studies (IVM) of the VU University of Amsterdam). The method was validated and used for the analysis of petroleum hydrocarbons extracted from refinery effluents. The report describes the technology transfer and the approaches used to demonstrate the successful transfer and application of the GCxGC methodology from analysing petroleum products to the quantitative determination of hydrocarbon blocks in refinery effluents. The report describes all the methods used for all the determinations on the effluent samples along with an overview of the results obtained which are presented in summary tables and graphs. These data have significantly improved CONCAWE's knowledge of what refineries emit in their effluents. A total of 111 Effluent Discharge Samples from 105 CONCAWE refineries in Europe were obtained in the period June 2008 to March 2009. These effluents were analysed for metals, standard effluent parameters (including COD, BOD), oil in water, BTEX and volatile organic compounds. The hydrocarbon speciation determinations and other hydrocarbon analyses are also reported. The individual refinery analytical results are included into this report, coded as per the CONCAWE system. These data will be, individually, communicated to companies and refineries. The report demonstrates that it is feasible to conduct a research programme to investigate the fate and effects of hydrocarbon blocks present in discharged refinery effluents.

  15. Sympatric Speciation in Threespine Stickleback: Why Not?

    Directory of Open Access Journals (Sweden)

    Daniel I. Bolnick

    2011-01-01

    Full Text Available Numerous theoretical models suggest that sympatric speciation is possible when frequency-dependent interactions such as intraspecific competition drive disruptive selection on a trait that is also subject to assortative mating. Here, I review recent evidence that both conditions are met in lake populations of threespine stickleback (Gasterosteus aculeatus. Nonetheless, sympatric speciation appears to be rare or absent in stickleback. If stickleback qualitatively fit the theoretical requirements for sympatric speciation, why do they not undergo sympatric speciation? I present simulations showing that disruptive selection and assortative mating in stickleback, though present, are too weak to drive speciation. Furthermore, I summarize empirical evidence that disruptive selection in stickleback drives other forms of evolutionary diversification (plasticity, increased trait variance, and sexual dimorphism instead of speciation. In conclusion, core assumptions of sympatric speciation theory seem to be qualitatively reasonable for stickleback, but speciation may nevertheless fail because of (i quantitative mismatches with theory and (ii alternative evolutionary outcomes.

  16. Contribution of neutron activation analysis and radioanalytical techniques to trace element speciation in environmental analysis

    International Nuclear Information System (INIS)

    Gallorini, M.; Orvini, E.; Sabbioni, E.; Pietra, R.

    1984-01-01

    The feasibility of the NAA in contributing to trace element speciation in environmental and biological samples is shown by a few selected applications. They are: (i) the determination of different species of vanadium, arsenic and selenium in freshwater. The pre-irradiation treatments in which the different chemical species are selectively isolated are critically evaluated. Problems arising from possible contaminations or losses and from blanks are discussed; (ii) the use of NAA in metallobiochemical speciation once biochemical methods of cellular fractionation for the isolation of metallobiocomplexes are developed. Examples concern the biochemical speciation of vanadium in human blood and the development of a method for speciation of inorganic and organic arsenic compounds in biological samples. The use of radioanalytical techniques in developing the separation procedures of different trace metal chemical and biochemical species is also briefly discussed. 24 references, 5 figures, 4 tables

  17. Neutral Models with Generalised Speciation

    NARCIS (Netherlands)

    Haegeman, Bart; Etienne, Rampal S.

    Hubbell's neutral theory claims that ecological patterns such as species abundance distributions can be explained by a stochastic model based on simple assumptions. One of these assumptions, the point mutation assumption, states that every individual has the same probability to speciate. Etienne et

  18. Mitochondrial Recombination and Introgression during Speciation by Hybridization.

    Science.gov (United States)

    Leducq, Jean-Baptiste; Henault, Mathieu; Charron, Guillaume; Nielly-Thibault, Lou; Terrat, Yves; Fiumera, Heather L; Shapiro, B Jesse; Landry, Christian R

    2017-08-01

    Genome recombination is a major source of genotypic diversity and contributes to adaptation and speciation following interspecies hybridization. The contribution of recombination in these processes has been thought to be largely limited to the nuclear genome because organelles are mostly uniparentally inherited in animals and plants, which prevents recombination. Unicellular eukaryotes such as budding yeasts do, however, transmit mitochondria biparentally, suggesting that during hybridization, both parents could provide alleles that contribute to mitochondrial functions such as respiration and metabolism in hybrid populations or hybrid species. We examined the dynamics of mitochondrial genome transmission and evolution during speciation by hybridization in the natural budding yeast Saccharomyces paradoxus. Using population-scale mitochondrial genome sequencing in two endemic North American incipient species SpB and SpC and their hybrid species SpC*, we found that both parental species contributed to the hybrid mitochondrial genome through recombination. We support our findings by showing that mitochondrial recombination between parental types is frequent in experimental crosses that recreate the early step of this speciation event. In these artificial hybrids, we observed that mitochondrial genome recombination enhances phenotypic variation among diploid hybrids, suggesting that it could play a role in the phenotypic differentiation of hybrid species. Like the nuclear genome, the mitochondrial genome can, therefore, also play a role in hybrid speciation. © The Author 2017. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  19. Mercury speciation with fluorescent gold nanocluster as a probe.

    Science.gov (United States)

    Yang, Jian-Yu; Yang, Ting; Wang, Xiao-Yan; Chen, Ming-Li; Yu, Yong-Liang; Wang, Jian-Hua

    2018-05-11

    Fluorescent nanoparticles are widely used for sensing biologically significant species. However, it is rarely reported for the discrimination or speciation of metal species. In this work, we report for the first time the speciation of mercury (Hg 2+ ) and methylmercury (CH 3 Hg + ) by taking advantage of the fluorescence feature of folic acid-capped gold nanoclusters (FA-AuNCs). FA-Au NCs exhibit an average size of 2.08±0.15 nm and a maximum emission at λ ex /λ em = 280/440 nm with a quantum yield of 27.3%. It is interesting that Hg 2+ causes a significant quench on the fluorescence of FA-Au NCs, whereas CH 3 Hg + leads to a remarkable fluorescence enhancement. Based on this discriminative fluorescent response between Hg 2+ and CH 3 Hg + , a novel nanosensor for the speciation of CH 3 Hg + and Hg 2+ was developed, providing limits of detection (LOD) of 28 nM for Hg 2+ and 25 nM for CH 3 Hg + within 100-1000 nM. This sensing system is highly selective to mercury. Its practical applications were further demonstrated by the analysis of CH 3 Hg + and the speciation of mercury (CH 3 Hg + and Hg 2+ ) in environmental water and fish samples.

  20. Interaction between Digestive Strategy and Niche Specialization Predicts Speciation Rates across Herbivorous Mammals.

    Science.gov (United States)

    Tran, Lucy A P

    2016-04-01

    Biotic and abiotic factors often are treated as mutually exclusive drivers of diversification processes. In this framework, ecological specialists are expected to have higher speciation rates than generalists if abiotic factors are the primary controls on species diversity but lower rates if biotic interactions are more important. Speciation rate is therefore predicted to positively correlate with ecological specialization in the purely abiotic model but negatively correlate in the biotic model. In this study, I show that the positive relationship between ecological specialization and speciation expected from the purely abiotic model is recovered only when a species-specific trait, digestive strategy, is modeled in the terrestrial, herbivorous mammals (Mammalia). This result suggests a more nuanced model in which the response of specialized lineages to abiotic factors is dependent on a biological trait. I also demonstrate that the effect of digestive strategy on the ecological specialization-speciation rate relationship is not due to a difference in either the degree of ecological specialization or the speciation rate between foregut- and hindgut-fermenting mammals. Together, these findings suggest that a biological trait, alongside historical abiotic events, played an important role in shaping mammal speciation at long temporal and large geographic scales.

  1. Differential Survival between Visual Environments Supports a Role of Divergent Sensory Drive in Cichlid Fish Speciation.

    Science.gov (United States)

    Maan, Martine E; Seehausen, Ole; Groothuis, Ton G G

    2017-01-01

    Identifying the selective forces that initiate ecological speciation is a major challenge in evolutionary biology. Sensory drive has been implicated in speciation in various taxa, largely based on phenotype-environment correlations and signatures of selection in sensory genes. Here, we present a reciprocal transplant experiment revealing species differences in performance in alternative visual environments, consistent with speciation by divergent sensory drive. The closely related cichlids Pundamilia pundamilia and Pundamilia nyererei inhabit different visual environments in Lake Victoria and show associated differences in visual system properties. Mimicking the two light environments in the laboratory, we find a substantial reduction in survival of both species when reared in the other species' visual environment. This implies that the observed differences in Pundamilia color vision are indeed adaptive and substantiates the implicit assumption in sensory drive speciation models that divergent environmental selection is strong enough to drive divergence in sensory properties.

  2. Root uptake of uranium (6) in solution by a higher plant: speciation in hydroponic solution, bioavailability, micro-localisation and biological effects induced; Transfert racinaire de l'uranium (6) en solution chez une plante superieure: speciation en solution hydroponique, prise en charge par la plante, microlocalisation et effets biologiques induits

    Energy Technology Data Exchange (ETDEWEB)

    Laroche, L

    2005-01-15

    Uranium exists naturally in the environment, usually present in trace quantities. In soil solution and oxic conditions, uranium is present in the +VI oxidation state and forms a large number of inorganic and organic complexes. The exposure medium, an artificial soil solution, was designed in such a way as to control the uranium species in solution. The geochemical speciation code JCHESS was used to calculate the uranium aqueous species concentration and to define the domains of interest, each of them characterized by a limited number of dominant U species. These domains were defined as follows: pH 4.9 with uranyl ions as dominant species, pH 5.8 with hydroxyl complexes and pH 7 where carbonates play a major role. For each pH, short-duration (5 hours of exposure) well-defined laboratory experiments were carried out with Phaseolus vulgaris as plant model. The effect of competitive ions such as Ca{sup 2+} or the presence of ligands such as phosphate or citrate on root assimilation efficiency was explored. Results have shown that uranium transfer was not affected by the presence of calcium, phosphate or citrate (but was decreased of 60% with citrate (10 {mu}M) at pH 5.8) in our experimental conditions. Moreover, observation in Transmission Electronic Microscopy (TEM), equipped with an EDAX probe, have shown that uranium was associated with granules rich in phosphorus and that there were some chloroplast anomalies. Finally, the presence of uranium affects root CEC by reducing it and stimulates root elongation at low uranium concentrations (100 nM, 400 nM and 2 {mu}M at pHs 4.9, 5.8 and 7 respectively) and inhibits it at high uranium concentrations. (author)

  3. Aspects of speciation in foodstuffs

    International Nuclear Information System (INIS)

    Crews, Helen M.

    2001-01-01

    Food is the primary source of trace elements for humans and it is now generally accepted that the bioavailability of a given element and its behaviour in the body depends upon its chemical form. This point was illustrated with the example of arsenic speciation in fish in which bioaccumulation takes place in the marine food chain, however, the species of arsenic ingested by man when the fish is consumed are not toxic. It was pointed out that species information will be vital in deciding upon realistic average dietary requirements for trace elements, particularly because both deficiency or excess of an element can have detrimental consequences on an individual's health. Two examples of speciation studies with food (Cd and Se) were presented and the importance of the use of label technology which will allow studies of target analytes at physiological levels, was stressed

  4. MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

    Science.gov (United States)

    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...

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

    Science.gov (United States)

    Maggi, F.; Riley, W. J.

    2009-12-01

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

  6. Behavioural divergence, interfertility and speciation: a review.

    Science.gov (United States)

    Pillay, Neville; Rymer, Tasmin L

    2012-11-01

    Behavioural compatibility between mates is fundamental for maintaining species boundaries and is achieved through appropriate communication between males and females. A breakdown in communication will lead to behavioural divergence and reduced interfertility. In this review, we summarise the current knowledge on male signals and female perception of these signals, integrating the literature from several taxa. We advocate that signaller-perceiver coevolution, which is usually under strong stabilising selection to enable mating, forms the basis of species-specific mate recognition systems. The mechanisms (phylogeny, geography, ecology, biology) shaping signaller-perceiver systems are briefly discussed to demonstrate the factors underpinning the evolution of signaller-perceiver couplings. Since divergence and diversification of communication systems is driven by changes in the mechanical properties of sensory pathways and morphology of sensory organs, we highlight signal modalities (auditory, olfactory, visual, tactile) and their importance in communication, particularly in mate selection. Next, using available examples and generating a stylised model, we suggest how disruption (biological, ecological, stochastic) of signaller-perceiver systems drives behavioural divergence and consequently results in reduced interfertility and speciation. Future studies should adopt an integrative approach, combining multiple parameters (phylogeny, adaptive utility of communication systems, genetics and biomechanical/biochemical properties of signals and perception) to explore how disruption of signaller-perceiver systems results in behavioural divergence and reduced interfertility. Finally, we question the impact that rapid environmental change will have on disruption of communication systems, potentially interfering with signaller-perceiver couplings. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. Uranium speciation in Fernald soils

    International Nuclear Information System (INIS)

    Morris, D.E.; Conradson, S.D.; Tait, C.D.; Chisholm-Brause, C.J.; Berg, J.; Musgrave, J.

    1992-01-01

    This report details progress made from January 1 to May 31, 1992 in this analytical support task to determine the speciation of uranium in contaminated soil samples from the Fernald Environmental Management Project site under the auspices of the Uranium in Soils Integrated Demonstration funded through the US DOE's Office of Technology Development. The authors' efforts have focused on characterization of soil samples collected by S.Y. Lee (Oak Ridge National Laboratory) from five locales at the Fernald site. These were chosen to sample a broad range of uranium source terms. On the basis of x-ray absorption spectroscopy data, they have determined that the majority of uranium (> 80--90%) exists in the hexavalent oxidation state for all samples examined. This is a beneficial finding from the perspective of remediation, because U(VI) species are more soluble in general than uranium species in other oxidation states. Optical luminescence data from many of the samples show the characteristic structured yellow-green emission from the uranyl (UO 2 2+ ) moiety. The luminescence data also suggest that much of the uranium in these soils is present as well-crystallized UO 2 2+ species. Some clear spectroscopic distinctions have been noted for several samples that illustrate significant differences in the speciation (1) from site to site, (2) within different horizons at the same site, and (3) within different size fractions of the soils in the same horizon at the same site. This marked heterogeneity in uranyl speciation suggests that several soil washing strategies may be necessary to reduce the total uranium concentrations within these soils to regulatory limits

  8. Speciation of Pb in industrially polluted soils

    DEFF Research Database (Denmark)

    Jensen, Pernille Erland; Ottosen, Lisbeth M.; Pedersen, Anne Juul

    2006-01-01

    This study was aimed at elucidating the importance of original Pb-speciation versus soil-characteristics to mobility and distribution of Pb in industrially polluted soils. Ten industrially polluted Danish surface soils were characterized and Pb speciation was evaluated through SEM-EDX studies...

  9. Speciation analysis of radionuclides in the environment. NKS-B speciation project report 2007

    Energy Technology Data Exchange (ETDEWEB)

    Xiaolin Hou (Technical Univ. of Denmark, Risoe National Lab. for Sustainable Energy, Roskilde (Denmark)); Aldahan, A. (Uppsala Univ., Dept. of Earth Science, Uppsala (Sweden)); Possnert, G. (Uppsala Univ., Tandem Lab., Uppsala (Sweden)); Lujaniene, G. (Institute of Physics, Vilnius (Lithuania)); Lehto, J. (Univ. of Helsinki, Dept. of Chemistry, Helsinki (Finland)); Salbu, B. (Norwegian Univ. of Life Sciences (UMB), AAs (Norway))

    2008-07-15

    This report describes the work carried out under the NUK-B project SPECIATION 2007. In 2007, the project partners had two meeting in April and November, organized a NUK seminar on speciation and hot particles. SPECIATION 2007 t mainly focused on two issues on speciation (1) further development of speciation methods for radionuclides, and (2) investigation of speciation of radionuclides in environment. The report summarized the work done in partners labs, which includes: (1) Further development on the speciation of 129I and 127I in water samples; (2) Speciation method for 129I and 127I in air; (3) Dynamic system for fractionation of Pu and Am in soil and sediment; (4) Investigation on Re-absorption of Pu during the fractionation of Pu in soil and sediment; (5) Speciation of 129I in North Sea surface water; (6) Partition of 137Cs and 129I in the Nordic lake sediment, pore-water and lake water; (7) Sequential extraction of Pu in soil, sediment and concrete samples, (8) Pu sorption to Mn and Fe oxides in the geological materials, (10) Investigation of the adsorbed species of lanthanides and actinides on clays surfaces. In addition, two review articles on the speciation of plutonium and iodine in environmental are planned to be submitted to an international journal for publication. (au)

  10. Speciation analysis of radionuclides in the environment. NKS-B speciation project report 2007

    International Nuclear Information System (INIS)

    Hou, Xiaolin; Aldahan, A.; Possnert, G.; Lujaniene, G.; Lehto, J.; Salbu, B.

    2008-07-01

    This report describes the work carried out under the NUK-B project SPECIATION 2007. In 2007, the project partners had two meeting in April and November, organized a NUK seminar on speciation and hot particles. SPECIATION 2007 t mainly focused on two issues on speciation (1) further development of speciation methods for radionuclides, and (2) investigation of speciation of radionuclides in environment. The report summarized the work done in partners labs, which includes: (1) Further development on the speciation of 129I and 127I in water samples; (2) Speciation method for 129I and 127I in air; (3) Dynamic system for fractionation of Pu and Am in soil and sediment; (4) Investigation on Re-absorption of Pu during the fractionation of Pu in soil and sediment; (5) Speciation of 129I in North Sea surface water; (6) Partition of 137Cs and 129I in the Nordic lake sediment, pore-water and lake water; (7) Sequential extraction of Pu in soil, sediment and concrete samples, (8) Pu sorption to Mn and Fe oxides in the geological materials, (10) Investigation of the adsorbed species of lanthanides and actinides on clays surfaces. In addition, two review articles on the speciation of plutonium and iodine in environmental are planned to be submitted to an international journal for publication. (au)

  11. Dispersal and speciation: The cross Atlantic relationship of two parasitic cnidarians

    DEFF Research Database (Denmark)

    Dnyansagar, Rohit; Zimmermann, Bob; Moran, Yehu

    2018-01-01

    How dispersal strategies impact the distribution of species and subsequent speciation events is a fundamental question in evolutionary biology. Sedentary benthic marine organisms, such as corals or sea anemones usually rely on motile larval stages for dispersal and therefore have a relatively res...

  12. US EPA's SPECIATE 4.4 Database: Development and Uses

    Science.gov (United States)

    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...

  13. Speciation Analysis of Radionuclides in the Environment - NSK-B SPECIATION project report 2009

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Aldahan, Ala; Possnert, Göran

    . Speciation of radionuclides in soils and sediments includes: Sequential extraction of radionuclides in sediments and of trace elements in soil samples. Sequential extraction of radionuclides in aerosols and particles has also been performed. Further-more, sorption experiments have been performed......, sediments, particles); and (3) Intercomparison excise for speciation analysis of radionu-clides in soil and sediment. This report summarizes the work completed in the project partners’ laboratories, Method developments include: Development of an rapid and in-suit separation method for the speciation...... analysis of 129I in seawater samples; Development of a simple method for the speciation analysis of 129I in fresh water and seawater samples; Development of an on-line HPLC-ICP-MS method for the direct speciation analysis of 127I in water and leachate samples; Speciation of radionuclides in water includes...

  14. Study of Np speciation in citrate medium

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L.; Den Auwer, C.; Ansoborlo, E.; Moisy, P. [CEA Valrho - DEN/DRCP/SCPS, Bagnols sur Ceze (France); Cote, G. [ENSP - LECA, UMR 7575, Paris (France)

    2007-07-01

    In the framework of the French Environmental Nuclear Toxicology program, additional experiments related to the decorporation of actinides are planned. Decorporation is the removal or release from target organs (bones, liver, kidney..), tissues or cells of radioactive material previously incorporated in them, using chelating agents or other administrated pharmaceutical agents. The contradictory data on the neptunium complexation behaviour within blood and its transfer to target organs, as well as the inefficiency of therapeutic treatments, led us to study the complexation of this element with biological constituents. Within this purpose, the in vitro behaviour of Np(IV) and Np(V) in simple media simulating biological fluids was studied. This study was more specifically focused on the behaviour of neptunium with citrate ion, which is an essential component in a number of metalloenzyme active sites. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np(V) with various acido-basic forms of the citrate anion was observed; regarding Np(IV), complexes with Cit{sup 3-} have been observed. From the quantitative study of these equilibria, the values of the absolute constants for the complexation of Np(IV) and Np(V) with citrate were determined. Concerning the stability of neptunium towards oxydo-reduction, it was confirmed that Np(VI) was very quickly reduced to Np(V) by the citrate anions, whereas Np(IV) was stable. In the case of Np(V), it was observed that, depending on the pH and the citrate concentration, Np(V) was unstable and was reduced to Np(IV). The E-pH diagrams, constructed using the stability constants determined in this study, showed that this instability was due to the Np(V) disproportionation. (orig.)

  15. Speciation analysis of radionuclides in the environment - NSK-B SPECIATION project report 2009

    International Nuclear Information System (INIS)

    Hou, X.; Aldahan, A.; Possnert, G.; Lujaniene, G.; Lehto, J.; Skipperud, L.; Lind, O.C.; Salbu, B.

    2009-10-01

    The second stage of the NKS-B project SPECIATION was complemented in 2008-2009, which mainly focus on three aspects: (1) Further improvement and development of methods for speciation analysis of radionuclides; (2) Investigation of speciation of some radionuclides in the environment (water, sediments, particles); and (3) Intercomparison excise for speciation analysis of radionuclides in soil and sediment. This report summarizes the work completed in the project partners' laboratories. Method developments include: Development of an rapid and in-suit separation method for the speciation analysis of 129I in seawater samples; Development of a simple method for the speciation analysis of 129I in fresh water and seawater samples; Development of an on-line HPLC-ICP-MS method for the direct speciation analysis of 127I in water and leachate samples; Speciation of radionuclides in water includes: Speciation of 129I and 127I in time-series precipitation samples collected in Denmark 2001-2006 and its application for the investigation of geochemistry and atmospheric chemistry of iodine, Speciation of radionuclides in Ob and Yenisey Rivers, and Speciation of 129I and 127I in Lake Heimdalen water. Speciation of radionuclides in soils and sediments includes: Sequential extraction of radionuclides in sediments and of trace elements in soil samples. Sequential extraction of radionuclides in aerosols and particles has also been performed. Furthermore, sorption experiments have been performed to investigate the association of Pu, Am and Cs with different geological materials. The intercomparison exercises included sequential extraction of Pu, 137Cs, U, Th, and 129I in one soil and one sediment standard reference materials (NIST-4354, IAEA-375) and Pu in sediment collected from the Lake Heimdalen, Norway. (author)

  16. Speciation analysis of radionuclides in the environment - NSK-B SPECIATION project report 2009

    Energy Technology Data Exchange (ETDEWEB)

    Hou, X. (Technical Univ. of Denmark, Risoe National Lab. for Sustainable Energy, Roskilde (Denmark)); Aldahan, A. (Uppsala Univ., Dept. of Earth Science (Sweden)); Possnert, G. (Uppsala Univ., Tandem Lab. (Sweden)); Lujaniene, G. (Univ. of Helsinki, Lab. of Radiochemistry (Finland)); Lehto, J. (Institute of Physics (Lithuania)); Skipperud, L.; Lind, O.C.; Salbu, B. (Norwegian Univ. of Life Sciences, Isotope Lab., AAs (Norway))

    2009-10-15

    The second stage of the NKS-B project SPECIATION was complemented in 2008-2009, which mainly focus on three aspects: (1) Further improvement and development of methods for speciation analysis of radionuclides; (2) Investigation of speciation of some radionuclides in the environment (water, sediments, particles); and (3) Intercomparison excise for speciation analysis of radionuclides in soil and sediment. This report summarizes the work completed in the project partners' laboratories. Method developments include: Development of an rapid and in-suit separation method for the speciation analysis of 129I in seawater samples; Development of a simple method for the speciation analysis of 129I in fresh water and seawater samples; Development of an on-line HPLC-ICP-MS method for the direct speciation analysis of 127I in water and leachate samples; Speciation of radionuclides in water includes: Speciation of 129I and 127I in time-series precipitation samples collected in Denmark 2001-2006 and its application for the investigation of geochemistry and atmospheric chemistry of iodine, Speciation of radionuclides in Ob and Yenisey Rivers, and Speciation of 129I and 127I in Lake Heimdalen water. Speciation of radionuclides in soils and sediments includes: Sequential extraction of radionuclides in sediments and of trace elements in soil samples. Sequential extraction of radionuclides in aerosols and particles has also been performed. Furthermore, sorption experiments have been performed to investigate the association of Pu, Am and Cs with different geological materials. The intercomparison exercises included sequential extraction of Pu, 137Cs, U, Th, and 129I in one soil and one sediment standard reference materials (NIST-4354, IAEA-375) and Pu in sediment collected from the Lake Heimdalen, Norway. (author)

  17. Radionuclide speciation in the environment: a review

    International Nuclear Information System (INIS)

    Moulin, V.; Moulin, C.

    2001-01-01

    Speciation determination is of prime importance to explain and evaluate the mobility, the toxicity and the risk resulting from the presence of trace elements in natural systems, in particular in the case of radionuclides, in the framework of environment and waste management purposes. The present paper will then focus more specifically on the physico-chemical speciation of radionuclides, and more particularly of actinides, in the environment, with emphasis on the behavior in solution: from a chemical point of view (with important ligands including colloidal phases) using experimental data and speciation calculations, as well as from a more technical point of view (with analytical methods for in situ speciation determination and thermodynamic data determination). A review of recent papers (mainly from CEA) is presented. (orig.)

  18. Pb speciation results in amended soils

    Data.gov (United States)

    U.S. Environmental Protection Agency — The dataset shows the distribution of Pb phases resulting from various amendments to change Pb speciation. This dataset is associated with the following publication:...

  19. Speciation of radionuclides in the environment

    International Nuclear Information System (INIS)

    Gunten, H.R. von; Benes, P.

    1994-02-01

    Methods for the determination of the speciation of radionuclides in aerosols, in aquatic solutions, in sediments, soils and rocks are reviewed. At present, most of the results about speciation are deduced from model calculations, model experiments, and separation of species (forms) of radionuclides, e.g., by sequential extraction procedures. Methods of direct determination of speciation of radionuclides (e.g. by laser induced spectroscopy) are in general not yet sensitive enough for a measurement of the very low concentrations of radionuclides in the environment. The methodological part of this paper is followed by a review of the very abundant literature about speciation of important radionuclides in the environment, i.e. in the atmosphere, hydrosphere and lithosphere. The review does not include the biosphere. Literature up to spring 1993 is included (with a few more recent additions). (author)

  20. Evolution: sympatric speciation the eusocial way

    DEFF Research Database (Denmark)

    Boomsma, Jacobus Jan; Nash, David Richard

    2014-01-01

    Sympatric speciation normally requires particular conditions of ecological niche differentiation. However, ant social parasites have been suspected to arise sympatrically, because (dis)loyalty to eusocial kin-structures induces disruptive selection for dispersal and inbreeding. A new study docume...

  1. Dearborn GC-MS organic speciation data

    Data.gov (United States)

    U.S. Environmental Protection Agency — Ambient particulate matter organic speciation data from July - August, 2011. This dataset is associated with the following publication: Lynam, M., T. Dvonch, J....

  2. Aerosol Chemical Speciation Monitor (ACSM) Instrument Handbook

    Energy Technology Data Exchange (ETDEWEB)

    Watson, Thomas B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2017-08-15

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) measures particle mass loading and chemical composition in real time for non-refractory sub-micron aerosol particles. The ACSM is designed for long-term unattended deployment and routine monitoring applications.

  3. Molecular Phylogenetics of the Serranid Subfamily Epinephelinae: Speciation and Biogeography in a Nearshore Marine Fish Clade

    OpenAIRE

    Craig, Matthew T,

    2005-01-01

    The processes that shape present day distributions of marine organisms have remained a central topic in evolutionary biology, conservation biology, and ecology. In this thesis, genetic data from mitochondrial and nuclear genes were used to create a phylogenetic hypothesis for the groupers of the subfamily Epinephelinae as a means of evaluating the current taxonomy of the group and the geography of speciation in marine organisms. The molecular phylogenetic hypothesis presented in Chap...

  4. Geography, assortative mating, and the effects of sexual selection on speciation with gene flow.

    Science.gov (United States)

    Servedio, Maria R

    2016-01-01

    Theoretical and empirical research on the evolution of reproductive isolation have both indicated that the effects of sexual selection on speciation with gene flow are quite complex. As part of this special issue on the contributions of women to basic and applied evolutionary biology, I discuss my work on this question in the context of a broader assessment of the patterns of sexual selection that lead to, versus inhibit, the speciation process, as derived from theoretical research. In particular, I focus on how two factors, the geographic context of speciation and the mechanism leading to assortative mating, interact to alter the effect that sexual selection through mate choice has on speciation. I concentrate on two geographic contexts: sympatry and secondary contact between two geographically separated populations that are exchanging migrants and two mechanisms of assortative mating: phenotype matching and separate preferences and traits. I show that both of these factors must be considered for the effects of sexual selection on speciation to be inferred.

  5. Research on the chemical speciation of actinides

    International Nuclear Information System (INIS)

    Jung, Euo Chang; Park, K. K.; Cho, H. R.

    2012-04-01

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using highly sensitive and advanced laser-based spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been applied for the chemical speciation of actinide in aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. Development of TRLFS technology for the chemical speciation of actinides, Development of laser-induced photo-acoustic spectroscopy (LPAS) system, Application of LIBD technology to investigate dynamic behaviors of actinides dissolution reactions, Development of nanoparticle analysis technology in groundwater using LIBD, Chemical speciation of plutonium complexes by using a LWCC system, Development of LIBS technology for the quantitative analysis of actinides, Evaluation on the chemical reactions between actinides and humic substances, Spectroscopic speciation of uranium-ligand complexes in aqueous solution, Chemical speciation of actinides adsorbed on metal oxides surfaces

  6. Research on the chemical speciation of actinides

    International Nuclear Information System (INIS)

    Jung, Euo Chang; Park, K. K.; Cho, H. R.

    2010-04-01

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using advanced laser-based highly sensitive spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been performed for the chemical speciation of actinide in an aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. (1) Development of TRLFS technology for chemical speciation of actinides, (2) Development of LIBD technology for measuring solubility of actinides, (3) Chemical speciation of plutonium complexes by using a LWCC system, (4) Development of LIBS technology for the quantitative analysis of actinides, (5) Development of technology for the chemical speciation of actinides by CE, (6) Evaluation on the chemical reactions between actinides and humic substances, (7) Chemical speciation of actinides adsorbed on metal oxides surfaces, (8) Determination of actinide source terms of spent nuclear fuel

  7. Selfish X chromosomes and speciation.

    Science.gov (United States)

    Patten, Manus M

    2017-12-27

    In two papers published at about the same time almost thirty years ago, Frank (Evolution, 45, 1991a, 262) and Hurst and Pomiankowski (Genetics, 128, 1991, 841) independently suggested that divergence of meiotic drive systems-comprising genes that cheat meiosis and genes that suppress this cheating-might provide a general explanation for Haldane's rule and the large X-effect in interspecific hybrids. Although at the time, the idea was met with skepticism and a conspicuous absence of empirical support, the tide has since turned. Some of the clearest mechanistic explanations we have for hybrid male sterility involve meiotic drive systems, and several other cases of hybrid sterility are suggestive of a role for meiotic drive. In this article, I review these ideas and their descendants and catalog the current evidence for the meiotic drive model of speciation. In addition, I suggest that meiotic drive is not the only intragenomic conflict to involve the X chromosome and contribute to hybrid incompatibility. Sexually and parentally antagonistic selection pressures can also pit the X chromosome and autosomes against each other. The resulting intragenomic conflicts should lead to co-evolution within populations and divergence between them, thus increasing the likelihood of incompatibilities in hybrids. I provide a sketch of these ideas and interpret some empirical patterns in the light of these additional X-autosome conflicts. © 2017 John Wiley & Sons Ltd.

  8. How Facilitation May Interfere with Ecological Speciation

    Directory of Open Access Journals (Sweden)

    P. Liancourt

    2012-01-01

    Full Text Available Compared to the vast literature linking competitive interactions and speciation, attempts to understand the role of facilitation for evolutionary diversification remain scarce. Yet, community ecologists now recognize the importance of positive interactions within plant communities. Here, we examine how facilitation may interfere with the mechanisms of ecological speciation. We argue that facilitation is likely to (1 maintain gene flow among incipient species by enabling cooccurrence of adapted and maladapted forms in marginal habitats and (2 increase fitness of introgressed forms and limit reinforcement in secondary contact zones. Alternatively, we present how facilitation may favour colonization of marginal habitats and thus enhance local adaptation and ecological speciation. Therefore, facilitation may impede or pave the way for ecological speciation. Using a simple spatially and genetically explicit modelling framework, we illustrate and propose some first testable ideas about how, when, and where facilitation may act as a cohesive force for ecological speciation. These hypotheses and the modelling framework proposed should stimulate further empirical and theoretical research examining the role of both competitive and positive interactions in the formation of incipient species.

  9. Speciation of zinc in contaminated soils

    International Nuclear Information System (INIS)

    Stephan, Chadi H.; Courchesne, Francois; Hendershot, William H.; McGrath, Steve P.; Chaudri, Amar M.; Sappin-Didier, Valerie; Sauve, Sebastien

    2008-01-01

    The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn 2+ , soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K d ) for Zn ranged from 17 to 13,100 L kg -1 soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn 2+ varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn 2+ , dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils. - We studied the relationships among the chemical speciation of Zn in soil solution extracts from 66 contaminated soils and various physicochemical properties of the soils

  10. Liquid phase microextraction for the analysis of trace elements and their speciation

    International Nuclear Information System (INIS)

    Hu, Bin; He, Man; Chen, Beibei; Xia, Linbo

    2013-01-01

    Trace/ultra-trace elements and their speciation analysis in complex matrices usually require sample preparation procedures to achieve sample clean-up and analyte preconcentration. Sample preparation is often the bottleneck in trace elements and their speciation analysis which has a direct impact on accuracy, precision and limits of detection and is often the rate-determining step of the analytical process. Recent trends in sample preparation include miniaturization, automation, high-throughput performance and reduction in solvent/sample consumption and operation time. Liquid-phase microextraction (LPME) technique as a novel and promising alternative in sample preparation can meet these requirements and has become a very efficient sample preparation technique. This review updates the state of art of LPME for trace elements and their speciation analysis and discusses its promising prospects. The major thrust of the article highlights the applications of LPME including single-drop microextraction (SDME), hollow fiber-liquid phase microextraction (HF-LPME), dispersive liquid liquid microextraction (DLLME) and solidified floating organic drop microextraction (SFODME) to the fields of elemental and their speciation analysis by atomic spectrometry-based methods, especially inductively coupled plasma mass spectrometry. General and specific concepts, different extraction formats and characteristics of LPME are described and compared, along with examples of recent innovations and applications presented to demonstrate its potential for trace elements and their speciation analysis in biological and environmental fields. Moreover, the application potential and an outlook on the combination of LPME and atomic spectrometry-based techniques for inorganic analysis are commentated. - Highlights: • The state of art of LPME for trace elements and their speciation analysis is updated. • Different extraction formats of LPME are described. • The application potential and future

  11. Iron(III) citrate speciation in aqueous solution.

    Science.gov (United States)

    Silva, Andre M N; Kong, XiaoLe; Parkin, Mark C; Cammack, Richard; Hider, Robert C

    2009-10-28

    Citrate is an iron chelator and it has been shown to be the major iron ligand in the xylem sap of plants. Furthermore, citrate has been demonstrated to be an important ligand for the non-transferrin bound iron (NTBI) pool occurring in the plasma of individuals suffering from iron-overload. However, ferric citrate chemistry is complicated and a definitive description of its aqueous speciation at neutral pH remains elusive. X-Ray crystallography data indicates that the alcohol function of citrate (Cit4-) is involved in Fe(III) coordination and that deprotonation of this functional group occurs upon complex formation. The inability to include this deprotonation in the affinity constant calculations has been a major source of divergence between various reports of iron(III)-citrate affinity constants. However the recent determination of the alcoholic pKa of citric acid (H4Cit) renders the reassessment of the ferric citrate system possible. The aqueous speciation of ferric citrate has been investigated by mass spectrometry and EPR spectroscopy. It was observed that the most relevant species are a monoiron dicitrate species and dinuclear and trinuclear oligomeric complexes, the relative concentration of which depends on the solution pH value and the iron : citric acid molar ratio. Spectrophotometric titration was utilized for affinity constant determination and the formation constant for the biologically relevant [Fe(Cit)2]5- is reported for the first time.

  12. Speciation from photon to ion detection

    International Nuclear Information System (INIS)

    Moulin, C.

    2001-01-01

    New analytical techniques allowing to perform speciation in the framework of the nuclear fuel cycle are more and more needed. Among them, several laser-based analytical techniques present several advantages (non intrusive). Hence, Thermal Lensing (TL)/Photoacoustic (LIPAS), Time Resolved selective, sensitive Laser-Induced Fluorescence (TRLIF) have been used for actinides/lanthanides interaction and speciation studies in inorganic and organic matrices, Laser Ablation-Optical Emission Spectroscopy (LA-OES or LIBS) for direct studies on solids, liquids,... where in situ measurements (elemental or isotopic) are mandatory. In complementary to these photon-based methods, new ion detection methods such as ElectroSpray-Mass Spectrometry (ES-MS) seems promising for speciation studies. Principle, advantages and limitations as well as results obtained and trends for these different methods will be presented. (author)

  13. Anaerobic Digestion Alters Copper and Zinc Speciation.

    Science.gov (United States)

    Legros, Samuel; Levard, Clément; Marcato-Romain, Claire-Emmanuelle; Guiresse, Maritxu; Doelsch, Emmanuel

    2017-09-19

    Anaerobic digestion is a widely used organic waste treatment process. However, little is known on how it could alter the speciation of contaminants in organic waste. This study was focused on determining the influence of anaerobic digestion on the speciation of copper and zinc, two metals that generally occur at high concentration in organic waste. Copper and zinc speciation was investigated by X-ray absorption spectroscopy in four different raw organic wastes (predigestion) and their digested counterparts (postdigestion, i.e., digestates). The results highlighted an increase in the digestates of the proportion of amorphous or nanostructured copper sulfides as well as amorphous or nanostructured zinc sulfides and zinc phosphate as compared to raw waste. We therefore suggest that the environmental fate of these elements would be different when spreading either digestates or raw waste on cropland.

  14. Loss of speciation rate will impoverish future diversity

    OpenAIRE

    Rosenzweig, Michael L.

    2001-01-01

    Human activities have greatly reduced the amount of the earth's area available to wild species. As the area they have left declines, so will their rates of speciation. This loss of speciation will occur for two reasons: species with larger geographical ranges speciate faster; and loss of area drives up extinction rates, thus reducing the number of species available for speciation. Theory predicts steady states in species diversity, and fossils suggest that these have t...

  15. The development of chemical speciation analysis

    International Nuclear Information System (INIS)

    Martin, R.; Santana, J.L.; Lima, L.; De La Rosa, D.; Melchor, K.

    2003-01-01

    The knowledge of many metals species on the environmental, its bioaccumulation, quantification and its effect in human body has been studied by a wide researchers groups in the last two decades. The development of speciation analysis has an vertiginous advance close to the developing of novel analytical techniques. Separation and quantification at low level is a problem that's has been afford by a coupling of high resolution chromatographic techniques like HPLC and HRGC with a specific method of detection (ICP-MS or CV-AAS). This methodological approach make possible the success in chemical speciation nowadays

  16. Incidence and Speciation of Candida Species among Non-gravid ...

    African Journals Online (AJOL)

    This study investigated the incidence and speciation of Candida species among non-gravid young females, using commercially available chromogenic Candida speciation media (CHROM agar) for the identification/speciation of medically important yeast and yeastlike organisms in a routine clinical mycology laboratory.

  17. EPAs SPECIATE 4.4 Database: Development and Uses

    Science.gov (United States)

    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...

  18. Actinide speciation in the environment

    International Nuclear Information System (INIS)

    Choppin, G.R.

    2007-01-01

    Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides are introduced into the aquatic system. Chemical speciation, oxidation state, redox reactions, and sorption characteristics are necessary in predicting solubility of the different actinides, their migration behaviors and their potential effects on marine biota. The most significant of these variables is the oxidation state of the metal ion as the simultaneous presence of more than one oxidation state for some actinides in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is much more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK sp ≥56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent UO 2 2+ in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(OH)(CO 3 ) is the limiting species for the solubility of Am(III) in sea water. Thorium(IV) is present as Th(OH) 4 , in colloidal form. The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in natural waters which must be considered in assessing the environmental behavior of actinides. Much is understood about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these radioactive species on marine biota, but much more understanding of the behavior of the actinides in the environment is

  19. Detecting cryptic speciation in the widespread and morphologically conservative carpet chameleon (Furcifer lateralis) of Madagascar.

    Science.gov (United States)

    Florio, A M; Ingram, C M; Rakotondravony, H A; Louis, E E; Raxworthy, C J

    2012-07-01

    Species delimitation within recently evolved groups can be challenging because species may be difficult to distinguish morphologically. Following the General Lineage Concept, we apply a multiple evidence approach to assess species limits within the carpet chameleon Furcifer lateralis, which is endemic to Madagascar and exported in large numbers for the pet trade. Cryptic speciation within F. lateralis was considered likely because this species (1) has a vast distribution, (2) occupies exceptionally diverse habitats and (3) exhibits subtle regional differences in morphology. Phylogenetic trees reconstructed using nuclear and mitochondrial genes recovered three well-supported clades corresponding with geography. Morphological results based on canonical variates analysis show that these clades exhibit subtle differences in head casque morphology. Ecological niche modelling results found that these phylogenetic groups also occupy unique environmental space and exhibit patterns of regional endemism typical of other endemic reptiles. Combined, our findings provide diverse yet consistent evidence for the existence of three species. Consequently, we elevate the subspecies F. lateralis major to species rank and name a new species distributed in northern and western Madagascar. Initial ecological divergence, associated with speciation of F. lateralis in humid eastern habitat, fits the Ecographic Constraint model for species diversification in Madagascar. By contrast, the second speciation event provides some support for the Riverine Barrier model, with the Mangoky River possibly causing initial isolation between species. These findings thus support two contrasting models of speciation within closely related species and demonstrate the utility of applying a combined-evidence approach for detecting cryptic speciation. © 2012 The Authors. Journal of Evolutionary Biology © 2012 European Society For Evolutionary Biology.

  20. Contemporary issues in evolutionary biology

    Indian Academy of Sciences (India)

    These discussions included, among others, the possible consequences of nonDNA-based inheritance—epigenetics and cultural evolution, niche construction, and developmental mechanisms on our understanding of the evolutionary process, speciation, complexity in biology, and constructing a formal evolutionary theory.

  1. A study of lead and cadmium speciation in some estuarine and coastal sediments

    Digital Repository Service at National Institute of Oceanography (India)

    Chakraborty, P.; Babu, P.V.R.; Sarma, V.V.

    ., Campbell, M., Weir, E., 2002, Identifying and managing adverse environmental health effects: 3. Lead exposure. CMAJ 166, 1287–1292. Stohs, S.J., Bagchi, D., 1995, Oxidative mechanisms in the toxicity of metal ions. Free Radical Biology and Medicine, 18... the kinetic speciation of Pb and Cd in the coastal and estuarine sediments of Bay of Bengal. Consider sediments samples of n different components, in which each component, M-Sediment i , exists in equilibrium with its dissociation products: the free metal...

  2. Early events in speciation: Polymorphism for hybrid male sterility in Drosophila

    OpenAIRE

    Reed, Laura K.; Markow, Therese A.

    2004-01-01

    Capturing the process of speciation early enough to determine the initial genetic causes of reproductive isolation remains a major challenge in evolutionary biology. We have found, to our knowledge, the first example of substantial intraspecific polymorphism for genetic factors contributing to hybrid male sterility. Specifically, we show that the occurrence of hybrid male sterility in crosses between Drosophila mojavensis and its sister species, Drosophila arizonae, is controlled by factors p...

  3. Electrochemical metal speciation in colloidal dispersions

    NARCIS (Netherlands)

    Wonders, J.H.A.M.

    1995-01-01

    The term "heavy metals" is connected with toxicity. They form strong complexes with enzymes, other proteins and DNA in living organisms, which causes dysfunctioning and hence poisoning. In combination with the uptake mechanism of the organism, speciation of heavy metal determines the

  4. ARSENIC SPECIATION ANALYSIS IN HUMAN SALIVA

    Science.gov (United States)

    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 ...

  5. Magic cues versus magic preferences in speciation

    NARCIS (Netherlands)

    Maan, Martine E.; Seehausen, Ole

    Question: How does divergent natural selection lead to divergence in mating traits and the evolution of reproductive isolation? Background: Ecological speciation of non-allopatric taxa usually requires the evolution of an association between selective mating and the traits underlying ecological

  6. Biogeochemical speciation of Fe in ocean water

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.

    2006-01-01

    The biogeochemical speciation of Fe in seawater has been evaluated using the consistent Non-Ideal Competitive Adsorption model (NICA¿Donnan model). Two types of data sets were used, i.e. Fe-hydroxide solubility data and competitive ligand equilibration/cathodic stripping voltammetry (CLE/CSV) Fe

  7. The speciation of iodine in the environment

    International Nuclear Information System (INIS)

    Bulman, R.A.

    1986-01-01

    The speciation of iodine in the environment is discussed under the following topics: (i) sea surface to atmosphere, (ii) chemistry in bulk seawater, (iii) iodine in rocks, (iv) iodine in soils, (v) iodine in plants and (vi) iodine in solidified wastes. (author)

  8. Multielemental speciation analysis by advanced hyphenated technique - HPLC/ICP-MS: A review.

    Science.gov (United States)

    Marcinkowska, Monika; Barałkiewicz, Danuta

    2016-12-01

    Speciation analysis has become an invaluable tool in human health risk assessment, environmental monitoring or food quality control. Another step is to develop reliable multielemental speciation methodologies, to reduce costs, waste and time needed for the analysis. Separation and detection of species of several elements in a single analytical run can be accomplished by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Our review assembles articles concerning multielemental speciation determination of: As, Se, Cr, Sb, I, Br, Pb, Hg, V, Mo, Te, Tl, Cd and W in environmental, biological, food and clinical samples analyzed with HPLC/ICP-MS. It addresses the procedures in terms of following issues: sample collection and pretreatment, selection of optimal conditions for elements species separation by HPLC and determination using ICP-MS as well as metrological approach. The presented work is the first review article concerning multielemental speciation analysis by advanced hyphenated technique HPLC/ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Mathematical modeling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation

    International Nuclear Information System (INIS)

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

    1998-01-01

    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. Mathematical modelling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation

    International Nuclear Information System (INIS)

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

    1998-01-01

    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 modelling 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 bioutilization 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 modelling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems. (orig.)

  11. Iron solubility driven by speciation in dust sources to the ocean

    Science.gov (United States)

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

    2009-01-01

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

  12. Polarographic validation of chemical speciation models

    International Nuclear Information System (INIS)

    Duffield, J.R.; Jarratt, J.A.

    2001-01-01

    It is well established that the chemical speciation of an element in a given matrix, or system of matrices, is of fundamental importance in controlling the transport behaviour of the element. Therefore, to accurately understand and predict the transport of elements and compounds in the environment it is a requirement that both the identities and concentrations of trace element physico-chemical forms can be ascertained. These twin requirements present the analytical scientist with considerable challenges given the labile equilibria, the range of time scales (from nanoseconds to years) and the range of concentrations (ultra-trace to macro) that may be involved. As a result of this analytical variability, chemical equilibrium modelling has become recognised as an important predictive tool in chemical speciation analysis. However, this technique requires firm underpinning by the use of complementary experimental techniques for the validation of the predictions made. The work reported here has been undertaken with the primary aim of investigating possible methodologies that can be used for the validation of chemical speciation models. However, in approaching this aim, direct chemical speciation analyses have been made in their own right. Results will be reported and analysed for the iron(II)/iron(III)-citrate proton system (pH 2 to 10; total [Fe] = 3 mmol dm -3 ; total [citrate 3- ] 10 mmol dm -3 ) in which equilibrium constants have been determined using glass electrode potentiometry, speciation is predicted using the PHREEQE computer code, and validation of predictions is achieved by determination of iron complexation and redox state with associated concentrations. (authors)

  13. Recent trends in nanomaterial-based microanalytical systems for the speciation of trace elements: A critical review.

    Science.gov (United States)

    Tseng, Wei-Chang; Hsu, Keng-Chang; Shiea, Christopher Stephen; Huang, Yeou-Lih

    2015-07-16

    Trace element speciation in biomedical and environmental science has gained increasing attention over the past decade as researchers have begun to realize its importance in toxicological studies. Several nanomaterials, including titanium dioxide nanoparticles (nano-TiO2), carbon nanotubes (CNTs), and magnetic nanoparticles (MNPs), have been used as sorbents to separate and preconcentrate trace element species prior to detection through mass spectrometry or optical spectroscopy. Recently, these nanomaterial-based speciation techniques have been integrated with microfluidics to minimize sample and reagent consumption and simplify analyses. This review provides a critical look into the present state and recent applications of nanomaterial-based microanalytical systems in the speciation of trace elements. The adsorption and preconcentration efficiencies, sample volume requirements, and detection limits of these nanomaterial-based speciation techniques are detailed, and their applications in environmental and biological analyses are discussed. Current perspectives and future trends into the increasing use of nanomaterial-based microfluidic techniques for trace element speciation are highlighted. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Speciation and zoogeography of amphibian in Sundaland

    Directory of Open Access Journals (Sweden)

    Nia Kurniawan

    2015-12-01

    Full Text Available Sundaland is an interesting area to be explored based on its geological history, topography, and climate. Sundaland consists of Penisular Malaysia, Sumatra, Borneo, and Java which experienced some emergence and submergence process in the past. During 1981-2015, most of research in Sundaland found that amphibian family in Sundaland was dominated by Bufonidae, Ranidae, Microhylidae, Megophrydae, Rachophoridae, and Dicroglossidae which experienced lot of speciation in its history. Among of 4 major islands in Sundaland, Borneo has the highest number of species diversity, then Peninsular Malaysia, Sumatra, and Java. During those years, Sumatra and Java got least concern by researcher. Therefore, it is suggested for further study to explore more in Sumatra and Java. Keywords: Sundaland, amphibian, speciation, zoogeography.

  15. Speciation studies of cobalt in sea water

    International Nuclear Information System (INIS)

    Toteja, R.S.D.; Sudersanan, M.; Iyer, R.K.

    1995-01-01

    Recent results on the speciation of cobalt in simulated and actual sea water is reported using ion exchangers. The influence of magnesium ions in affecting the composition of ion exchangers and subsequent interpretation of the results is discussed. The results indicated that Co +2 may predominate in both the simulated and actual sea water and the presence of other constituents in sea water does not affect the nature of complex species present. (author). 2 refs., 3 tabs., 1 fig

  16. Tungsten Speciation in Firing Range Soils

    Science.gov (United States)

    2011-01-01

    satisfactorily, such as: which tungsten mineral phase is present in soil and to what extent is adsorption important in regu- lating soil solution concentrations... soil solution rather than discrete mineral phases. Information provided in this report will assist the following organizations in future decision...the soil solution ERDC TR-11-1 43 must affect tungsten speciation in other ways. The precipitation of soil minerals also would limit tungsten

  17. The genetics of speciation by reinforcement.

    Directory of Open Access Journals (Sweden)

    Daniel Ortiz-Barrientos

    2004-12-01

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

  18. First passage time to allopatric speciation.

    Science.gov (United States)

    Yamaguchi, Ryo; Iwasa, Yoh

    2013-12-06

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

  19. Arsenic speciation and sorption in natural environments

    Science.gov (United States)

    Campbell, Kate M.; Nordstrom, D. Kirk

    2014-01-01

    Aqueous arsenic speciation, or the chemical forms in which arsenic exists in water, is a challenging, interesting, and complicated aspect of environmental arsenic geochemistry. Arsenic has the ability to form a wide range of chemical bonds with carbon, oxygen, hydrogen, and sulfur, resulting in a large variety of compounds that exhibit a host of chemical and biochemical properties. Besides the intriguing chemical diversity, arsenic also has the rare capacity to capture our imaginations in a way that few elements can duplicate: it invokes images of foul play that range from sinister to comedic (e.g., “inheritance powder” and arsenic-spiked elderberry wine). However, the emergence of serious large-scale human health problems from chronic arsenic exposure in drinking water has placed a high priority on understanding environmental arsenic mobility, toxicity, and bioavailability, and chemical speciation is key to these important questions. Ultimately, the purpose of arsenic speciation research is to predict future occurrences, mitigate contamination, and provide successful management of water resources.

  20. Incipient speciation driven by hypertrophied lips in Midas cichlid fishes?

    Science.gov (United States)

    Machado-Schiaffino, Gonzalo; Kautt, Andreas F; Torres-Dowdall, Julian; Baumgarten, Lukas; Henning, Frederico; Meyer, Axel

    2017-04-01

    Sympatric speciation has been debated in evolutionary biology for decades. Although it has gained in acceptance recently, still only a handful of empirical examples are seen as valid (e.g. crater lake cichlids). In this study, we disentangle the role of hypertrophied lips in the repeated adaptive radiations of Nicaraguan crater lake cichlid fish. We assessed the role of disruptive selection and assortative mating during the early stages of divergence and found a functional trade-off in feeding behaviour between thick- and thin-lipped ecotypes, suggesting that this trait is a target of disruptive selection. Thick-lipped fish perform better on nonevasive prey at the cost of a poorer performance on evasive prey. Using enclosures in the wild, we found that thick-lipped fish perform significantly better in rocky than in sandy habitats. We found almost no mixed pairs during two breeding seasons and hence significant assortative mating. Genetic differentiation between ecotypes seems to be related to the time since colonization, being subtle in L. Masaya (1600 generations ago) and absent in the younger L. Apoyeque (<600 generations ago). Genome-wide differentiation between ecotypes was higher in the old source lakes than in the young crater lakes. Our results suggest that hypertrophied lips might be promoting incipient sympatric speciation through divergent selection (ecological divergence in feeding performance) and nonrandom mating (assortative mating) in the young Nicaraguan crater lakes. Nonetheless, further manipulative experiments are needed in order to confirm the role of hypertrophied lips as the main cue for assortative mating. © 2017 John Wiley & Sons Ltd.

  1. Transformation of metals speciation in a combined landfill leachate treatment

    International Nuclear Information System (INIS)

    Wu Yanyu; Zhou Shaoqi; Chen Dongyu; Zhao Rong; Li Huosheng; Lin Yiming

    2011-01-01

    Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter > 0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction < 0.45 μm were considered as dissolved. - Research Highlights: → Metals in various landfill leachate treatments were size charge fractionated and the speciation transformations were compared. → Species predictions of metals were simulated by Visual MINTEQ model. → Optimum agreements for the free ion/labile species were within acidic solution. → Predictions of colloidal species agree with experimental data well in alkaline solution.

  2. Influence of Organic Matter - Mineral Interfacial Reactions on Metal(loid) Speciation and Bioaccessibility

    Science.gov (United States)

    Chorover, J.; Kong, S.; Root, R. A.; Thomas, A.

    2015-12-01

    Bioaccessibility of contaminant metals in geomedia is often measured on the basis of kinetic release to solution during in vitro reaction with biofluid simulants. We postulate that development of a predictive-mechanistic understanding of bioaccessibility requires knowledge of metal(loid) molecular speciation upon sample introduction, as well as its change over the course of the in vitro reaction. Our results - including data from batch, column, mesocosm and field studies pertaining to arsenic, lead, and zinc contaminated materials - indicate the strong influence of organic matter and associated biological activity on metal(loid) speciation in mine tailings and related model systems. Furthermore, presence/absence of organic matter during bioassays affects the kinetics of metal(loid) release into biofluid simulants through multiple mechanisms.

  3. Trace-element speciation and partitioning in environmental geochemistry and health

    Energy Technology Data Exchange (ETDEWEB)

    Farmer, J.G.; Gibson, M.J.; Lovell, M.A.

    1983-09-01

    Establishment of the chemical form and associations of trace elements is important in the scientifc and medical fields related to environmental geochemistry and health. Fundamental understanding of trace-element behavior, the realistic formulation of historical perspectives of trace-element contamination, an assessment of environmental transformation processes and a thorough appraisal of environment-related ill health and disease all depend on knowledge of the chemical speciation and partitioning of trace elements. These topics and the development of analytical speciation techniques and procedures are discussed with reference to trace-element studies in the Department of Forensic Medicine and Science, University of Glasgow, on lacustrine sediments and water, the atmosphere, soil and street dirt of an urban environment, and human biological fluids. 206 references, 4 figures.

  4. Electrospray mass spectrometry for actinides and lanthanide speciation

    International Nuclear Information System (INIS)

    Moulin, C.; Amekraz, B.; Colette, S.; Doizi, D.; Jacopin, C.; Lamouroux, C.; Plancque, G.

    2006-01-01

    Electrospray mass spectrometry (ES-MS) is a new speciation technique that has the great interest to be able to probe the element, the ligand and the complex in order to reach the speciation. This paper will focus on the use of ES-MS for the speciation of actinides/lanthanides on several systems of interest in various fields such as the interaction between DTPA (decorporant) and europium, HEBP and uranium, BTP (new extracting agent) and lanthanides with comparison with known chemistry as well as whenever possible with other speciation techniques

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

    International Nuclear Information System (INIS)

    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. Rapid allopatric speciation in logperch darters (Percidae: Percina).

    Science.gov (United States)

    Near, Thomas J; Benard, Michael F

    2004-12-01

    Theory predicts that clades diversifying via sympatric speciation will exhibit high diversification rates. However, the expected rate of diversification in clades characterized by allopatric speciation is less clear. Previous studies have documented significantly higher speciation rates in freshwater fish clades diversifying via sympatric versus allopatric modes, leading to suggestions that the geographic pattern of speciation can be inferred solely from knowledge of the diversification rate. We tested this prediction using an example from darters, a clade of approximately 200 species of freshwater fishes endemic to eastern North America. A resolved phylogeny was generated using mitochondrial DNA gene sequences for logperches, a monophyletic group of darters composed of 10 recognized species. Divergence times among logperch species were estimated using a fossil calibrated molecular clock in centrarchid fishes, and diversification rates in logperches were estimated using several methods. Speciation events in logperches are recent, extending from 4.20 +/- 1.06 million years ago (mya) to 0.42 +/- 0.22 mya, with most speciation events occurring in the Pleistocene. Diversification rates are high in logperches, at some nodes exceeding rates reported for well-studied adaptive radiations such as Hawaiian silverswords. The geographic pattern of speciation in logperches was investigated by examining the relationship between degree of sympatry and the absolute age of the contrast, with the result that diversification in logperches appears allopatric. The very high diversification rate observed in the logperch phylogeny is more similar to freshwater fish clades thought to represent examples of sympatric speciation than to clades representing allopatric speciation. These results demonstrate that the geographic mode of speciation for a clade cannot be inferred from the diversification rate. The empirical observation of high diversification rates in logperches demonstrates that

  7. Complementary arsenic speciation methods: A review

    Energy Technology Data Exchange (ETDEWEB)

    Nearing, Michelle M., E-mail: michelle.nearing@rmc.ca; Koch, Iris, E-mail: koch-i@rmc.ca; Reimer, Kenneth J., E-mail: reimer-k@rmc.ca

    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 arsenic-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. - Highlights: • HPLC–ICP-MS is the most common method used for arsenic speciation. • HPLC limitations include

  8. Plutonium Speciation, Solubilization and Migration in Soils

    International Nuclear Information System (INIS)

    Neu, M.; Runde, W.

    1999-01-01

    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

  9. Complementary arsenic speciation methods: A review

    International Nuclear Information System (INIS)

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

    2014-01-01

    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 arsenic-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. - Highlights: • HPLC–ICP-MS is the most common method used for arsenic speciation. • HPLC limitations include

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

    NARCIS (Netherlands)

    Leeuwen, van H.P.; Town, R.M.; Buffle, J.; Cleven, R.F.M.J.; Davison, W.; Puy, J.; Riemsdijk, van W.H.; Sigg, L.

    2005-01-01

    Dynamic metal speciation analysis in aquatic ecosystems is emerging as a powerful basis for development of predictions of bioavailability and reliable risk assessment strategies. A given speciation sensor is characterized by an effective time scale or kinetic window that defines the measurable metal

  11. Parasites Promote and When Might They Constrain Ecological Speciation?

    Directory of Open Access Journals (Sweden)

    Anssi Karvonen

    2012-01-01

    Full Text Available Research on speciation and adaptive radiation has flourished during the past decades, yet factors underlying initiation of reproductive isolation often remain unknown. Parasites represent important selective agents and have received renewed attention in speciation research. We review the literature on parasite-mediated divergent selection in context of ecological speciation and present empirical evidence for three nonexclusive mechanisms by which parasites might facilitate speciation: reduced viability or fecundity of immigrants and hybrids, assortative mating as a pleiotropic by-product of host adaptation, and ecologically-based sexual selection. We emphasise the lack of research on speciation continuums, which is why no study has yet made a convincing case for parasite driven divergent evolution to initiate the emergence of reproductive isolation. We also point interest towards selection imposed by single versus multiple parasite species, conceptually linking this to strength and multifariousness of selection. Moreover, we discuss how parasites, by manipulating behaviour or impairing sensory abilities of hosts, may change the form of selection that underlies speciation. We conclude that future studies should consider host populations at variable stages of the speciation process, and explore recurrent patterns of parasitism and resistance that could pinpoint the role of parasites in imposing the divergent selection that initiates ecological speciation.

  12. Self-consistent approach for neutral community models with speciation

    NARCIS (Netherlands)

    Haegeman, Bart; Etienne, Rampal S.

    Hubbell's neutral model provides a rich theoretical framework to study ecological communities. By incorporating both ecological and evolutionary time scales, it allows us to investigate how communities are shaped by speciation processes. The speciation model in the basic neutral model is

  13. The neutral theory of biodiversity with random fission speciation

    NARCIS (Netherlands)

    Etienne, Rampal S.; Haegeman, Bart

    The neutral theory of biodiversity and biogeography emphasizes the importance of dispersal and speciation to macro-ecological diversity patterns. While the influence of dispersal has been studied quite extensively, the effect of speciation has not received much attention, even though it was already

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-12-31

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

  15. Speciation and bioavailability of Americium-241 in the fresh water environment

    International Nuclear Information System (INIS)

    Bierkens, J.

    1986-01-01

    Due to its anthropogenic origin, the transuranic americium 241 confronts physiologists with the intriguing question, which mechanisms are involved in the incorporation or elimination of such artificial elements in biological cycles. The investigations on the speciation and bioavailability of 241 Am in the freshwater environment aim to establish a relation between the behavior of 241 Am in freshwater ecosystems and its availability for biota. In the limnic environment, most often characterized by a high organic load and a low conductivity, the effect of complexation of 241 Am with humic acids and competition with trivalent cations such as A1 and Fe, were proven to be significant on the speciation of 241 Am. Based on the registration of the 241 Am uptake by a large number of freshwater organisms, the crayfish Astacus leptodactylus Eschscholtz was chosen to study the whole-body uptake of 241 Am, its corresponding organ distribution and its retention in the animal. The share of external fixation and ingestion in the global uptake, and the effect of speciation on it, were studied more carefully. Other aspects in this physiological part were: the kinetics of 241 Am in the hemolymph and the hepatopancreas, and its subcellular distribution in the digestive gland. Finally, by comparing the physiology of 241 Am with some other metals ( 240 Pu, 64 Cu, 198 Au) with analogous or contradictional properties, we tried to find out whether the behavior of 241 Am in organisms can be explained from its chemical characteristics

  16. The variability in iron speciation in size fractionated residual oil fly ash particulate matter (ROFA PM).

    Science.gov (United States)

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

    2016-08-15

    Ambient particulate matter (PM) containing iron can catalyze Fenton reaction leading to the production of reactive oxygen species in cells. It can also catalyze atmospheric redox reaction. These reactions are governed by the physicochemical characteristics of iron in ambient PM. As a surrogate for ambient PM, we prepared residual oil fly ash PM (ROFA PM) in a practical fire tube boiler firing residual oils with varying sulfur and ash contents. The ROFA particles were resolved into fine PM or PM2.5 (aerodynamic diameter (AD)iron speciation in PM2.5+ was ascertained using X-ray absorption spectroscopy and leaching method while that in PM2.5 was reported earlier. The results of both studies are compared to get an insight into the variability in the iron speciation in different size fractions. The results show the predominance of ferric sulfate, with a minor spinal ferrite in both PM (i.e. ZnxNi1-xFe2O4 in PM2.5, ZnFe2O4 in PM2.5+). The iron solubility in ROFA PM depends on its speciation, mode of incorporation of iron into particle's carbonaceous matrix, the grade and composition of oils, and pH of the medium. The soluble fraction of iron in PM is critical in assessing its interaction with the biological systems and its toxic potential. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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. Copyright © 2010 Elsevier Ltd. All rights reserved.

  18. Early events in speciation: Cryptic species of Drosophila aldrichi.

    Science.gov (United States)

    Castro Vargas, Cynthia; Richmond, Maxi Polihronakis; Ramirez Loustalot Laclette, Mariana; Markow, Therese Ann

    2017-06-01

    Understanding the earliest events in speciation remains a major challenge in evolutionary biology. Thus identifying species whose populations are beginning to diverge can provide useful systems to study the process of speciation. Drosophila aldrichi , a cactophilic fruit fly species with a broad distribution in North America, has long been assumed to be a single species owing to its morphological uniformity. While previous reports either of genetic divergence or reproductive isolation among different D. aldrichi strains have hinted at the existence of cryptic species, the evolutionary relationships of this species across its range have not been thoroughly investigated. Here we show that D. aldrichi actually is paraphyletic with respect to its closest relative, Drosophila wheeleri , and that divergent D. aldrichi lineages show complete hybrid male sterility when crossed. Our data support the interpretation that there are at least two species of D. aldrichi, making these flies particularly attractive for studies of speciation in an ecological and geographical context.

  19. Speciation imperatives for waste management and environmental pollution

    International Nuclear Information System (INIS)

    Wymer, R.G.

    2001-01-01

    This paper addresses speciation requirements in the context of problems produced by nuclear energy and nuclear weapons production. These problems are primarily in the areas of waste management, material contamination, and environmental pollution. They pose difficult and important measurement and speciation challenges. Examples of speciation requirements in the context of national and international regulations are presented to exemplify and make quantitative the types of problems posed by waste management, material contamination, and environmental pollution. The importance of identifying species present in the natural environment as well as in wastes from chemical and physical processing and from waste management activities and accidental releases is addressed. Differing speciation requirements for macro and micro concentrations of species are discussed. The role of speciation in modelling studies is discussed. (author)

  20. Review and needs in actinide chemistry in relation with biological purposes

    Energy Technology Data Exchange (ETDEWEB)

    Ansoborlo, E.; Moulin, V.; Bion, L.; Doizi, D.; Moulin, C.; Cote, G.; Madic, C.; Van der Lee, J

    2004-07-01

    In case of accidental release of radionuclides in the environment, actinides could occur and may present an healthy risk for human beings. In order to study their behavior in human organism (metabolism, retention, excretion), it is of prime importance to know solution actinide chemistry, and more particularly thermodynamic constants, which will allow to determine their speciation: speciation governs biological availability and toxicity of elements and is also of great interest for decorporation purposes. In this framework, a CEA working group on speciation has been created in order to share data both on thermodynamic constants and on speciation analytical methods, interesting chemists, environmentalists and biologists. It has been focused, in a first time, on actinides. The purpose of this paper is to present the state of the art on actinide speciation within biological media and to focus on the lack of information in order to orientate future research. (authors)

  1. The rate test of speciation: estimating the likelihood of non-allopatric speciation from reproductive isolation rates in Drosophila.

    Science.gov (United States)

    Yukilevich, Roman

    2014-04-01

    Among the most debated subjects in speciation is the question of its mode. Although allopatric (geographical) speciation is assumed the null model, the importance of parapatric and sympatric speciation is extremely difficult to assess and remains controversial. Here I develop a novel approach to distinguish these modes of speciation by studying the evolution of reproductive isolation (RI) among taxa. I focus on the Drosophila genus, for which measures of RI are known. First, I incorporate RI into age-range correlations. Plots show that almost all cases of weak RI are between allopatric taxa whereas sympatric taxa have strong RI. This either implies that most reproductive isolation (RI) was initiated in allopatry or that RI evolves too rapidly in sympatry to be captured at incipient stages. To distinguish between these explanations, I develop a new "rate test of speciation" that estimates the likelihood of non-allopatric speciation given the distribution of RI rates in allopatry versus sympatry. Most sympatric taxa were found to have likely initiated RI in allopatry. However, two putative candidate species pairs for non-allopatric speciation were identified (5% of known Drosophila). In total, this study shows how using RI measures can greatly inform us about the geographical mode of speciation in nature. © 2013 The Author(s). Evolution © 2013 The Society for the Study of Evolution.

  2. Relative Bioavailability and Bioaccessability and Speciation of ...

    Science.gov (United States)

    Background: Assessment of soil arsenic (As) bioavailability may profoundly affect the extent of remediation required at contaminated sites by improving human exposure estimates. Because small adjustments in soil As bioavailability estimates can significantly alter risk assessments and remediation goals, convenient, rapid, reliable, and inexpensive tools are needed to determine soil As bioavailability. Objectives: We evaluated inexpensive methods for assessing As bioavailability in soil as a means to improve human exposure estimates and potentially reduce remediation costs. Methods: Nine soils from residential sites affected by mining or smelting activity and two National Institute of Standards and Technology standard reference materials were evaluated for As bioavailability, bioaccessibility, and speciation. Arsenic bioavailability was determined using an in vivo mouse model, and As bioaccessibility was determined using the Solubility/Bioavailability Research Consortium in vitro assay. Arsenic speciation in soil and selected soil physicochemical properties were also evaluated to determine whether these parameters could be used as predictors of As bio¬availability and bioaccessibility. Results: In the mouse assay, we compared bioavailabilities of As in soils with that for sodium arsenate. Relative bioavailabilities (RBAs) of soil As ranged from 11% to 53% (mean, 33%). In vitro soil As bioaccessibility values were strongly correlated with soil As RBAs (R

  3. Uranium(VI) speciation by spectroscopy

    International Nuclear Information System (INIS)

    Meinrath, G.

    1997-01-01

    The application of UV-Vis and time-resolved laser-induced fluorescence (TRLF) spectroscopies to direct of uranium(VI) in environmental samples offers various prospects that have, however, serious limitations. While UV-Vis spectroscopy is probably not sensitive enough to detect uranium(VI) species in the majority of environmental samples, TRLFS is principially able to speciate uranium(VI) at very low concentration levels in the nanomol range. Speciation by TRLFS can be based on three parameters: excitation spectrum, emission spectrum and lifetime of the fluorescence emission process. Due to quenching effects, the lifetime may not be expected to be as characteristics as, e.g., the emission spectrum. Quenching of U(VI) fluorescence by reaction with organic substances, inorganic ions and formation of carbonate radicals is one important limiting factor in the application of U(VI) fluorescence spectroscopy. Fundamental photophysical criteria are illustrated using UV-Vis and fluorescence spectra of U(VI) hydrolysis and carbonato species as examples. (author)

  4. Resolving uncertainty in chemical speciation determinations

    Science.gov (United States)

    Smith, D. Scott; Adams, Nicholas W. H.; Kramer, James R.

    1999-10-01

    Speciation determinations involve uncertainty in system definition and experimentation. Identification of appropriate metals and ligands from basic chemical principles, analytical window considerations, types of species and checking for consistency in equilibrium calculations are considered in system definition uncertainty. A systematic approach to system definition limits uncertainty in speciation investigations. Experimental uncertainty is discussed with an example of proton interactions with Suwannee River fulvic acid (SRFA). A Monte Carlo approach was used to estimate uncertainty in experimental data, resulting from the propagation of uncertainties in electrode calibration parameters and experimental data points. Monte Carlo simulations revealed large uncertainties present at high (>9-10) and low (monoprotic ligands. Least-squares fit the data with 21 sites, whereas linear programming fit the data equally well with 9 sites. Multiresponse fitting, involving simultaneous fluorescence and pH measurements, improved model discrimination. Deconvolution of the excitation versus emission fluorescence surface for SRFA establishes a minimum of five sites. Diprotic sites are also required for the five fluorescent sites, and one non-fluorescent monoprotic site was added to accommodate the pH data. Consistent with greater complexity, the multiresponse method had broader confidence limits than the uniresponse methods, but corresponded better with the accepted total carboxylic content for SRFA. Overall there was a 40% standard deviation in total carboxylic content for the multiresponse fitting, versus 10% and 1% for least-squares and linear programming, respectively.

  5. Chromium fractionation and speciation in natural waters.

    Science.gov (United States)

    Pereira, Catarinie Diniz; Techy, João Gabriel; Ganzarolli, Edgard Moreira; Quináia, Sueli Pércio

    2012-05-01

    It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.

  6. Speciation of animal fat: Needs and challenges.

    Science.gov (United States)

    Hsieh, Yun-Hwa Peggy; Ofori, Jack Appiah

    2017-05-24

    The use of pork fat is a concern for Muslims and Jews, who for religious reasons avoid consuming anything that is pig-derived. The use of bovine materials, including beef fat, is prohibited in Hinduism and may also pose a risk of carrying the infectious agent for bovine spongiform encephalopathy. Vegetable oils are sometimes adulterated with animal fat or pork fat with beef fat for economic gain. The development of methods to determine the species origin of fat has therefore become a priority due to the complex and global nature of the food trade, which creates opportunities for the fraudulent use of these animal fats as food ingredients. However, determining the species origin of fats in processed foods or composite blends is an arduous task as the adulterant has a composition that is very similar to that of the original fat or oil. This review examines some of the methods that have been developed for fat speciation, including both fat-based and DNA-based methods, their shortcomings, and the need for additional alternatives. Protein-based methods, specifically immunoassays targeting residual proteins in adipose tissue, that are being explored by researchers as a new tool for fat speciation will also be discussed.

  7. Co-Speciation of the Ectoparasite Gyrodactylus teuchis (Monogenea, Platyhelminthes and Its Salmonid Hosts.

    Directory of Open Access Journals (Sweden)

    Christoph Hahn

    Full Text Available Co-speciation is a fundamental concept of evolutionary biology and intuitively appealing, yet in practice hard to demonstrate as it is often blurred by other evolutionary processes. We investigate the phylogeographic history of the monogenean ectoparasites Gyrodactylus teuchis and G. truttae on European salmonids of the genus Salmo. Mitochondrial cytochrome oxidase subunit 1 and the nuclear ribosomal internal transcribed spacer 2 were sequenced for 189 Gyrodactylus individuals collected from 50 localities, distributed across most major European river systems, from the Iberian- to the Balkan Peninsula. Despite both anthropogenic and naturally caused admixture of the principal host lineages among major river basins, co-phylogenetic analyses revealed significant global congruence for host and parasite phylogenies, providing firm support for co-speciation of G. teuchis and its salmonid hosts brown trout (S. trutta and Atlantic salmon (S. salar. The major split within G. teuchis, coinciding with the initial divergence of the hosts was dated to ~1.5 My BP, using a Bayesian framework based on an indirect calibration point obtained from the host phylogeny. The presence of G. teuchis in Europe thus predates some of the major Pleistocene glaciations. In contrast, G. truttae exhibited remarkably low intraspecific genetic diversity. Given the direct life cycle and potentially high transmission potential of gyrodactylids, this finding is interpreted as indication for a recent emergence (<60 ky BP of G. truttae via a host-switch. Our study thus suggests that instances of two fundamentally different mechanisms of speciation (co-speciation vs. host-switching may have occurred on the same hosts in Europe within a time span of less than 1.5 My in two gyrodactylid ectoparasite species.

  8. Speciation below ground: Tempo and mode of diversification in a radiation of endogean ground beetles.

    Science.gov (United States)

    Andújar, Carmelo; Pérez-González, Sergio; Arribas, Paula; Zaballos, Juan P; Vogler, Alfried P; Ribera, Ignacio

    2017-11-01

    Dispersal is a critical factor determining the spatial scale of speciation, which is constrained by the ecological characteristics and distribution of a species' habitat and the intrinsic traits of species. Endogean taxa are strongly affected by the unique qualities of the below-ground environment and its effect on dispersal, and contrasting reports indicate either high dispersal capabilities favoured by small body size and mediated by passive mechanisms, or low dispersal due to restricted movement and confinement inside the soil. We studied a species-rich endogean ground beetle lineage, Typhlocharina, including three genera and more than 60 species, as a model for the evolutionary biology of dispersal and speciation in the deep soil. A time-calibrated molecular phylogeny generated from >400 individuals was used to delimit candidate species, to study the accumulation of lineages through space and time by species-area-age relationships and to determine the geographical structure of the diversification using the relationship between phylogenetic and geographic distances across the phylogeny. Our results indicated a small spatial scale of speciation in Typhlocharina and low dispersal capacity combined with sporadic long distance, presumably passive dispersal events that fuelled the speciation process. Analysis of lineage growth within Typhlocharina revealed a richness plateau correlated with the range of distribution of lineages, suggesting a long-term species richness equilibrium mediated by density dependence through limits of habitat availability. The interplay of area- and age-dependent processes ruling the lineage diversification in Typhlocharina may serve as a general model for the evolution of high species diversity in endogean mesofauna. © 2017 John Wiley & Sons Ltd.

  9. Speciation in Metal Toxicity and Metal-Based Therapeutics

    Directory of Open Access Journals (Sweden)

    Douglas M. Templeton

    2015-04-01

    Full Text Available Metallic elements, ions and compounds produce varying degrees of toxicity in organisms with which they come into contact. Metal speciation is critical to understanding these adverse effects; the adjectives “heavy” and “toxic” are not helpful in describing the biological properties of individual elements, but detailed chemical structures are. As a broad generalization, the metallic form of an element is inert, and the ionic salts are the species that show more significant bioavailability. Yet the salts and other chelates of a metal ion can give rise to quite different toxicities, as exemplified by a range of carcinogenic potential for various nickel species. Another important distinction comes when a metallic element is organified, increasing its lipophilicity and hence its ability to penetrate the blood brain barrier, as is seen, for example, with organic mercury and tin species. Some metallic elements, such as gold and platinum, are themselves useful therapeutic agents in some forms, while other species of the same element can be toxic, thus focusing attention on species interconversions in evaluating metal-based drugs. The therapeutic use of metal-chelating agents introduces new species of the target metal in vivo, and this can affect not only its desired detoxification, but also introduce a potential for further mechanisms of toxicity. Examples of therapeutic iron chelator species are discussed in this context, as well as the more recent aspects of development of chelation therapy for uranium exposure.

  10. Maternal-foetal genomic conflict and speciation: no evidence for hybrid placental dysplasia in crosses between two house mouse subspecies

    Czech Academy of Sciences Publication Activity Database

    Kropáčková, L.; Piálek, Jaroslav; Gergelits, Václav; Forejt, Jiří; Reifová, R.

    2015-01-01

    Roč. 28, č. 3 (2015), s. 688-698 ISSN 1010-061X R&D Projects: GA ČR GA13-08078S Institutional support: RVO:68081766 ; RVO:68378050 Keywords : hybrid placental dysplasia * genomic conflicts * speciation * X chromosome * house mouse * Mus musculus musculus * Mus musculus domesticus Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.747, year: 2015

  11. A Z-linked sterility locus causes sexual abstinence in hybrid females and facilitates speciation in Spodoptera frugiperda

    Czech Academy of Sciences Publication Activity Database

    Kost, S.; Heckel, D. G.; Yoshido, Atsuo; Marec, František; Groot, A. T.

    2016-01-01

    Roč. 70, č. 6 (2016), s. 1418-1427 ISSN 0014-3820 R&D Projects: GA ČR(CZ) GA14-22765S Grant - others:European Union Seventh Framework Programme (FP7/2007-2013)(CZ) 316304 Program:FP7 Institutional support: RVO:60077344 Keywords : hybrid sterility * sex chromosome * speciation Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 4.201, year: 2016 http://onlinelibrary.wiley.com/doi/10.1111/evo.12940/abstract

  12. Sulphur-binding in recent environments. II. Speciation of sulphur and iron and implications for the occurrence of organo-sulphur compounds

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hartgers, W.A.; Lopez, J.F.; Reiss, C.; Maxwell, J.R.; Grimalt, J.O.

    1997-01-01

    Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron

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

    Science.gov (United States)

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

    2016-02-01

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

  14. EPA’s SPECIATE 4.4 Database:Development and Uses

    Science.gov (United States)

    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...

  15. Sexual selection and magic traits in speciation with gene flow

    Directory of Open Access Journals (Sweden)

    Maria R. SERVEDIO, Michael KOPP

    2012-06-01

    Full Text Available The extent to which sexual selection is involved in speciation with gene flow remains an open question and the subject of much research. Here, we propose that some insight can be gained from considering the concept of magic traits (i.e., traits involved in both reproductive isolation and ecological divergence. Both magic traits and other, “non-magic”, traits can contribute to speciation via a number of specific mechanisms. We argue that many of these mechanisms are likely to differ widely in the extent to which they involve sexual selection. Furthermore, in some cases where sexual selection is present, it may be prone to inhibit rather than drive speciation. Finally, there are a priori reasons to believe that certain categories of traits are much more effective than others in driving speciation. The combination of these points suggests a classification of traits that may shed light on the broader role of sexual selection in speciation with gene flow. In particular, we suggest that sexual selection can act as a driver of speciation in some scenarios, but may play a negligible role in potentially common categories of magic traits, and may be likely to inhibit speciation in common categories of non-magic traits [Current Zoology 58 (3: 507–513, 2012].

  16. NICKEL SPECIATION OF URBAN PARTICULATE MATTER

    Energy Technology Data Exchange (ETDEWEB)

    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. Selenium speciation from farm to faeces

    International Nuclear Information System (INIS)

    Larsen, E.H.; Kapolna, E.; Hillestroem, P.R.; Laursen, K.; Budek, A.; Husted, S.; Buegel, S.

    2009-01-01

    Full text:The content and speciation of Se were studied in food crops originating from organic and conventional cultivation schemes. Additionally, carrots and onions were biofortified and intrinsically labelled using foliar spraying with isotopically enriched 77 SeO 3 -2 . HPLC-ICPMS and HPLC-ESIMS/MS analysis revealed that Se was mainly metabolized to 77 SeMet and to Me 77 SeCys, also in carrot. The 77 Se plants were processed to food (50 μg 77 Se/d) for a human intervention study. The isotopic enrichment by 77 Se as well as 67 Zn and 65 Cu in urine and faeces was determined by ICP(DRC)MS and the mineral absorption rates estimated. (author)

  18. Chemical speciation of radionuclides migrating in groundwaters

    International Nuclear Information System (INIS)

    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., 60 Co and 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

  19. Sex chromosomes and speciation in Drosophila

    Science.gov (United States)

    Presgraves, Daven C.

    2010-01-01

    Two empirical rules suggest that sex chromosomes play a special role in speciation. The first is Haldane's rule— the preferential sterility and inviability of species hybrids of the heterogametic (XY) sex. The second is the disproportionately large effect of the X chromosome in genetic analyses of hybrid sterility. Whereas the causes of Haldane's rule are well established, the causes of the ‘large X-effect’ have remained controversial. New genetic analyses in Drosophila confirm that the X is a hotspot for hybrid male sterility factors, providing a proximate explanation for the large X-effect. Several other new findings— on faster X evolution, X chromosome meiotic drive, and the regulation of the X chromosome in the male-germline— provide plausible evolutionary explanations for the large X-effect. PMID:18514967

  20. Speciation of actinides in marine waters

    International Nuclear Information System (INIS)

    Roberts, R.A.

    1984-01-01

    The oxidation state distribution of plutonium in seawater, pore water from marine sediments, and a series of model solutions similar to seawater was measured using a TTA solvent extraction technique and α liquid scintillation counting methods. Electromigration was used to compare migration behavior of americium in 0.7M NaCl solutions (pH 6.5 to 8.0) with the behavior calculated from predicted speciation. In all pH 8 solutions studied, Pu(VI) was rapidly reduced to Pu(V). In 0.7M NaCl, pH 8.0, and artifical seawater (no organics), the Pu(V) formed was stable. In real seawater (with organic components), a rapid reduction of Pu(VI) to Pu(IV) was also observed. The Pu(V) formed in seawater was metastable; a very slow reduction to Pu(IV) occurred. This reduction was catalyzed by light. Humic acid (obtained from marine sediments from the Bahama Islands), was added to 0.7M NaCl, pH 8.0 solutions to determine its effect on Pu redox reactions. The effect was similar to the reductions in seawater. Increasing the humic acid concentration decreased the amount of Pu(V) which was formed and favored the IV state. The americium electromigration experiments showed a +0.12 net charge for the Am complexes formed in 0.7M NaCl solutions from pH 7.0 to 8.0. This value was smaller than the charge of +0.94 calculated from predicted speciation

  1. Isolation-by-distance and outbreeding depression are sufficient to drive parapatric speciation in the absence of environmental influences.

    Directory of Open Access Journals (Sweden)

    Guy A Hoelzer

    Full Text Available A commonly held view in evolutionary biology is that speciation (the emergence of genetically distinct and reproductively incompatible subpopulations is driven by external environmental constraints, such as localized barriers to dispersal or habitat-based variation in selection pressures. We have developed a spatially explicit model of a biological population to study the emergence of spatial and temporal patterns of genetic diversity in the absence of predetermined subpopulation boundaries. We propose a 2-D cellular automata model showing that an initially homogeneous population might spontaneously subdivide into reproductively incompatible species through sheer isolation-by-distance when the viability of offspring decreases as the genomes of parental gametes become increasingly different. This simple implementation of the Dobzhansky-Muller model provides the basis for assessing the process and completion of speciation, which is deemed to occur when there is complete postzygotic isolation between two subpopulations. The model shows an inherent tendency toward spatial self-organization, as has been the case with other spatially explicit models of evolution. A well-mixed version of the model exhibits a relatively stable and unimodal distribution of genetic differences as has been shown with previous models. A much more interesting pattern of temporal waves, however, emerges when the dispersal of individuals is limited to short distances. Each wave represents a subset of comparisons between members of emergent subpopulations diverging from one another, and a subset of these divergences proceeds to the point of speciation. The long-term persistence of diverging subpopulations is the essence of speciation in biological populations, so the rhythmic diversity waves that we have observed suggest an inherent disposition for a population experiencing isolation-by-distance to generate new species.

  2. saosakwe@yahoo.com Chemical Speciation and Mobility of Some

    African Journals Online (AJOL)

    Michael Horsfall

    ABSTRACT: The mobility of some heavy metals (Fe, Co, Ni and Mn) in soils around ... Sampling and Analysis: Soil samples were collected ..... Speciation Studies of trace elements levels in .... Characterization of Radioactive Particles in the.

  3. Pb Speciation Data to Estimate Lead Bioavailability to Quail

    Data.gov (United States)

    U.S. Environmental Protection Agency — Linear combination fitting data for lead speciation of soil samples evaluated through an in-vivo/in-vitro correlation for quail exposure. This dataset is associated...

  4. Speciation and Persistence of Dimethoate in the Aquatic Environment

    African Journals Online (AJOL)

    Speciation and Persistence of Dimethoate in the Aquatic Environment: Characterization in Terms of a Rate Model that Takes Into Account Hydrolysis, Photolysis, Microbial Degradation and Adsorption of the Pesticide by Colloidal and Sediment Particles.

  5. Genomic support for speciation and specificity of baculoviruses

    NARCIS (Netherlands)

    Jakubowska, A.K.

    2010-01-01

    Keywords: baculovirus, insects, speciation, genomics, phylogeny, host specificity

    The Baculoviridae comprise a large family of double-stranded DNA viruses infecting
    arthropods. In this thesis two baculoviruses, Leucoma salicis nucleopolyhedrovirus
    (LesaNPV) and Agrotis

  6. Speciation of long-lived radionuclides in the environment

    Energy Technology Data Exchange (ETDEWEB)

    Xiaolin Hou

    2008-11-15

    This project started in November 2005 and ended in November 2008, the work and research approaches are summarized in this report. This project studied the speciation of radionuclides in environment. A number of speciation analytical methods are developed for determination of species of 129I, 99Tc, isotopes of Pu, and 237Np in seawater, fresh water, soil, sediment, vegetations, and concrete. The developed methods are used for the investigation of the chemical speciation of these radionuclides as well as their environmental behaviours, especially in Danish environment. In addition the speciation of Pu isotopes in waste samples from the decommissioning of Danish nuclear facilities is also investigated. The report summarizes these works completed in this project. Through this research project, a number of research papers have been published in the scientific journals, the research results has also been presented in the Nordic and international conference/meeting and communicated to international colleagues. Some publications are also enclosed to this report. (au)

  7. Chemical speciation of long-lived radionuclides in the environment

    International Nuclear Information System (INIS)

    Xiaolin Hou

    2008-11-01

    This project started in November 2005 and ended in November 2008, the work and research approaches are summarized in this report. This project studied the speciation of radionuclides in environment. A number of speciation analytical methods are developed for determination of species of 129 I, 99 Tc, isotopes of Pu, and 237 Np in seawater, fresh water, soil, sediment, vegetations, and concrete. The developed methods are used for the investigation of the chemical speciation of these radionuclides as well as their environmental behaviours, especially in Danish environment. In addition the speciation of Pu isotopes in waste samples from the decommissioning of Danish nuclear facilities is also investigated. The report summarizes these works completed in this project. Through this research project, a number of research papers have been published in the scientific journals, the research results has also been presented in the Nordic and international conference/meeting and communicated to international colleagues. Some publications are also enclosed to this report. (au)

  8. Infectious speciation revisited: impact of symbiont-depletion on female fitness and mating behavior of Drosophila paulistorum.

    Directory of Open Access Journals (Sweden)

    Wolfgang J Miller

    2010-12-01

    Full Text Available The neotropical Drosophila paulistorum superspecies, consisting of at least six geographically overlapping but reproductively isolated semispecies, has been the object of extensive research since at least 1955, when it was initially trapped mid-evolution in flagrant statu nascendi. In this classic system females express strong premating isolation patterns against mates belonging to any other semispecies, and yet uncharacterized microbial reproductive tract symbionts were described triggering hybrid inviability and male sterility. Based on theoretical models and limited experimental data, prime candidates fostering symbiont-driven speciation in arthropods are intracellular bacteria belonging to the genus Wolbachia. They are maternally inherited symbionts of many arthropods capable of manipulating host reproductive biology for their own benefits. However, it is an ongoing debate as to whether or not reproductive symbionts are capable of driving host speciation in nature and if so, to what extent. Here we have reevaluated this classic case of infectious speciation by means of present day molecular approaches and artificial symbiont depletion experiments. We have isolated the α-proteobacteria Wolbachia as the maternally transmitted core endosymbionts of all D. paulistorum semispecies that have coevolved towards obligate mutualism with their respective native hosts. In hybrids, however, these mutualists transform into pathogens by overreplication causing embryonic inviability and male sterility. We show that experimental reduction in native Wolbachia titer causes alterations in sex ratio, fecundity, and mate discrimination. Our results indicate that formerly designated Mycoplasma-like organisms are most likely Wolbachia that have evolved by becoming essential mutualistic symbionts in their respective natural hosts; they have the potential to trigger pre- and postmating isolation. Furthermore, in light of our new findings, we revisit the concept of

  9. The reality and importance of founder speciation in evolution.

    Science.gov (United States)

    Templeton, Alan R

    2008-05-01

    A founder event occurs when a new population is established from a small number of individuals drawn from a large ancestral population. Mayr proposed that genetic drift in an isolated founder population could alter the selective forces in an epistatic system, an observation supported by recent studies. Carson argued that a period of relaxed selection could occur when a founder population is in an open ecological niche, allowing rapid population growth after the founder event. Selectable genetic variation can actually increase during this founder-flush phase due to recombination, enhanced survival of advantageous mutations, and the conversion of non-additive genetic variance into additive variance in an epistatic system, another empirically confirmed prediction. Templeton combined the theories of Mayr and Carson with population genetic models to predict the conditions under which founder events can contribute to speciation, and these predictions are strongly confirmed by the empirical literature. Much of the criticism of founder speciation is based upon equating founder speciation to an adaptive peak shift opposed by selection. However, Mayr, Carson and Templeton all modeled a positive interaction of selection and drift, and Templeton showed that founder speciation is incompatible with peak-shift conditions. Although rare, founder speciation can have a disproportionate importance in adaptive innovation and radiation, and examples are given to show that "rare" does not mean "unimportant" in evolution. Founder speciation also interacts with other speciation mechanisms such that a speciation event is not a one-dimensional process due to either selection alone or drift alone. (c) 2008 Wiley Periodicals, Inc.

  10. Electrochemical metal speciation in natural and model polyelectrolyte systems

    OpenAIRE

    Hoop, van den, M.A.G.T.

    1994-01-01

    The purpose of the research described in this thesis was to examine the applicability of electro-analytical techniques in obtaining information on the speciation of metals, i.e. their distribution over different physico-chemical forms, in aquatic systems containing charged macromolecules. In chapter 1 a general introduction is given to (i) metal speciation in aquatic systems, (ii) (bio)polyelectrolytes and their counterion distributions and (iii) electrochemical ...

  11. How humans drive speciation as well as extinction

    DEFF Research Database (Denmark)

    Bull, Joseph William; Maron, M.

    2016-01-01

    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....

  12. Self-consistent approach for neutral community models with speciation

    Science.gov (United States)

    Haegeman, Bart; Etienne, Rampal S.

    2010-03-01

    Hubbell’s neutral model provides a rich theoretical framework to study ecological communities. By incorporating both ecological and evolutionary time scales, it allows us to investigate how communities are shaped by speciation processes. The speciation model in the basic neutral model is particularly simple, describing speciation as a point-mutation event in a birth of a single individual. The stationary species abundance distribution of the basic model, which can be solved exactly, fits empirical data of distributions of species’ abundances surprisingly well. More realistic speciation models have been proposed such as the random-fission model in which new species appear by splitting up existing species. However, no analytical solution is available for these models, impeding quantitative comparison with data. Here, we present a self-consistent approximation method for neutral community models with various speciation modes, including random fission. We derive explicit formulas for the stationary species abundance distribution, which agree very well with simulations. We expect that our approximation method will be useful to study other speciation processes in neutral community models as well.

  13. Investigation of actinides speciation within the presence of ligands of interest for decorporation

    International Nuclear Information System (INIS)

    Bonin, L.

    2008-01-01

    Data about the behaviour of actinides in biological media are required in order to investigate their decorporation. Those data are obtained through in vivo experiments and the study of chemical speciation of actinides within the presence of biological constituents. A part of this work consists in the development of a method leading to the determination of the speciation of actinides at the oxidation state +IV within the presence of a complexing species, as well as its structure. The method was applied to two types of ligands: 1) a constituent of blood plasma: the citrate anion. The various complexes formed were investigated and their formation constants were quantified. The coordination mode of the ligand was then clarified through a structural study of the complexes, underlining the role of only one carboxylic site and of the alcohol function. 2) chelating agents used for decorporation. The formation constants of complexes of An(IV) with NTA and DTPA were determined. The coordination number of the metallic cation in those complexes as well as the role of the nitrogen atom were proved. Lastly, the behaviour of Pu(IV) within the presence of LIHOPO was investigated. This chelating agent, more efficient than DTPA in the case of in vivo decorporation of Np, forms very stable complexes with the metallic cation. One of those complexes can be assumed to present a stoichiometry 2:3. (author)

  14. Theoretical models of the influence of genomic architecture on the dynamics of speciation.

    Science.gov (United States)

    Flaxman, Samuel M; Wacholder, Aaron C; Feder, Jeffrey L; Nosil, Patrik

    2014-08-01

    A long-standing problem in evolutionary biology has been determining whether and how gradual, incremental changes at the gene level can account for rapid speciation and bursts of adaptive radiation. Using genome-scale computer simulations, we extend previous theory showing how gradual adaptive change can generate nonlinear population transitions, resulting in the rapid formation of new, reproductively isolated species. We show that these transitions occur via a mechanism rooted in a basic property of biological heredity: the organization of genes in genomes. Genomic organization of genes facilitates two processes: (i) the build-up of statistical associations among large numbers of genes and (ii) the action of divergent selection on persistent combinations of alleles. When a population has accumulated a critical amount of standing, divergently selected variation, the combination of these two processes allows many mutations of small effect to act synergistically and precipitously split one population into two discontinuous, reproductively isolated groups. Periods of allopatry, chromosomal linkage among loci, and large-effect alleles can facilitate this process under some conditions, but are not required for it. Our results complement and extend existing theory on alternative stable states during population divergence, distinct phases of speciation and the rapid emergence of multilocus barriers to gene flow. The results are thus a step towards aligning population genomic theory with modern empirical studies. © 2014 John Wiley & Sons Ltd.

  15. Uranium Speciation and Bioavailability in Aquatic Systems: An Overview

    Directory of Open Access Journals (Sweden)

    Scott J. Markich

    2002-01-01

    Full Text Available The speciation of uranium (U in relation to its bioavailability is reviewed for surface waters (fresh- and seawater and their sediments. A summary of available analytical and modeling techniques for determining U speciation is also presented. U(VI is the major form of U in oxic surface waters, while U(IV is the major form in anoxic waters. The bioavailability of U (i.e., its ability to bind to or traverse the cell surface of an organism is dependent on its speciation, or physicochemical form. U occurs in surface waters in a variety of physicochemical forms, including the free metal ion (U4+ or UO22+ and complexes with inorganic ligands (e.g., uranyl carbonate or uranyl phosphate, and humic substances (HS (e.g., uranyl fulvate in dissolved, colloidal, and/or particulate forms. Although the relationship between U speciation and bioavailability is complex, there is reasonable evidence to indicate that UO22+ and UO2OH+ are the major forms of U(VI available to organisms, rather than U in strong complexes (e.g., uranyl fulvate or adsorbed to colloidal and/or particulate matter. U(VI complexes with inorganic ligands (e.g., carbonate or phosphate and HS apparently reduce the bioavailability of U by reducing the activity of UO22+ and UO2OH+. The majority of studies have used the results from thermodynamic speciation modeling to support these conclusions. Time-resolved laser-induced fluorescence spectroscopy is the only analytical technique able to directly determine specific U species, but is limited in use to freshwaters of low pH and ionic strength. Nearly all of the available information relating the speciation of U to its bioavailability has been derived using simple, chemically defined experimental freshwaters, rather than natural waters. No data are available for estuarine or seawater. Furthermore, there are no available data on the relationship between U speciation and bioavailability in sediments. An understanding of this relationship has been

  16. Speciation of An(IV) (Pu, Np, U and Th) in citrate media

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L.; Moisy, P. [CEA Valrho, DEN/DRCP/SCPS/LCA, Bagnols sur Ceze (France); Cote, G. [Ecole Nationale Superieure de Chimie, 75 - Paris (France)

    2008-07-01

    The acquisition of additional data concerning actinide decorporation is planned under the French nuclear and environmental toxicology program. Citric acid is a fundamental biological constituent found at relatively high concentrations in blood plasma and is involved in many biological processes. Spectrophotometry was the primary method used to determine the speciation of An(IV)-citrate systems (Th, U, Np, Pu). Complexation phenomena were identified, especially the formation of complexes with 1:1 and 1:2 stoichiometries. The corresponding conditional constants were calculated according to the experimental conditions. Depending on the acid-base form of the ligand (H{sub 2}Cit{sup -}, HCit{sup 2-} or Cit{sup 3-}) the apparent stability constants were also calculated and compared for various tetravalent actinides. (orig.)

  17. Evolutionary pets: offspring numbers reveal speciation process in domesticated chickens.

    Directory of Open Access Journals (Sweden)

    Inga Tiemann

    Full Text Available Since Darwin, the nature of the relationship between evolution and domestication has been debated. Evolution offers different mechanisms of selection that lead to adaptation and may end in the origin of new species as defined by the biological species concept. Domestication has given rise to numerous breeds in almost every domesticated species, including chickens. At the same time, so-called artificial selection seems to exclude mechanisms of sexual selection by the animals themselves. We want to forward the question to the animal itself: With whom do you reproduce successfully? This study focused on the sexual behavior of the domestic chicken Gallus gallus f.dom., particularly the White Crested Polish breed. Experiments on mate choice and the observation of fertilization and hatching rates of mixed-breeding groups revealed breed-specific preferences. In breeding groups containing White Crested Polish and a comparative breed, more purebred chicks hatched than hybrids (number of eggs collected: 1059. Mating was possible in equal shares, but in relation to the number of eggs collected, purebred offspring (62.75% ± 7.10%, M ± SE hatched to a greater extend compared to hybrid offspring (28.75% ± 15.32%, M ± SE. These data demonstrate that the mechanism of sexual selection is still present in domestic chicken breeds, which includes the alteration of gene frequencies typical for domestication and evolutionary speciation. Due to selection and mate choice we state that breeding in principle can generate new species. Therefore, we see domestication as an evolutionary process that integrates human interests of animal breeding with innate mate choice by the animal.

  18. Molecular activation analysis for chemical speciation studies

    International Nuclear Information System (INIS)

    Chai-Chifang

    1998-01-01

    The term of Molecular Activation Analysis (MAA) refers to an activation analysis method that is able to provide information about the chemical species of elements in system of interests, though its definition has remained to be assigned. Its development is strongly stimulated by the urgent need to know the chemical species of elements, because the total concentrations are often without any meaning when assessing health or environmental risks of trace elements.In practice, the MAA is a combination of conventional instrumental or radiochemical activation analysis and physical, chemical or biochemical separation techniques. The MAA is able to play a particular role in speciation studies. However, the critical point in the MAA is that it is not permitted to change the primitive chemical species of elements in systems, or the change has to be under control; in the meantime it is not allowed to form the 'new artifact' originally not present in systems. Some practical examples of MAA for chemical species research performed recently in our laboratory will be presented as follows: Chemical species of platinum group elements in sediment; Chemical species of iodine in marine algae; Chemical species of mercury in human tissues; Chemical species of selenium in corn; Chemical species of rare earth elements in natural plant, etc. The merits and limitations of MAA will be described as well. (author)

  19. Guidelines for terms related to chemical speciations and fractionation of elements : definitions, structural aspects, and methodological approaches (IUPAC Recommendations 2000)

    NARCIS (Netherlands)

    Templeton, D.M.; Ariese, F.; Cornelis, R.; Danielsson, L.G.; Muntau, H.; Leeuwen, van H.P.; Lobínski, R.

    2000-01-01

    This paper presents definitions of concepts related to speciation of elements, more particularly speciation analysis and chemical species. Fractionation is distinguished from speciation analysis, and a general outline of fractionation procedures is given. We propose a categorization of species

  20. Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

    Energy Technology Data Exchange (ETDEWEB)

    Boiteau, Rene M.; Shaw, Jared B.; Pasa Tolic, Ljiljana; Koppenaal, David W.; Jansson, Janet K.

    2018-05-01

    Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. Even small structural differences

  1. Estimation of Speciation and Distribution of {sup 131}I in urban and natural Environments

    Energy Technology Data Exchange (ETDEWEB)

    Hormann, Volker; Fischer, Helmut W. [University of Bremen, Institute of Environmental Physics, Otto-Hahn-Allee 1, 28359 Bremen (Germany)

    2014-07-01

    {sup 131}I is a radionuclide that may be introduced into natural and urban environments via several pathways. As a result of nuclear accidents it may be washed out from air or settle onto the ground by dry deposition. In urban landscapes this is again washed out by rain, partly introduced into the sewer system and thus transported to the next wastewater plant where it may accumulate in certain compartments. In rural landscapes it may penetrate the soil and be more or less available to plant uptake depending on chemical and physical conditions. On a regular basis, {sup 131}I is released into the urban sewer system in the course of therapeutic and diagnostic treatment of patients with thyroid diseases. The speciation of iodine in the environment is complex. Depending on redox state and biological activity, it may appear as I{sup -}, IO{sub 3}{sup -}, I{sub 2} or bound to organic molecules (e.g. humic acids). Moreover, some of these species are bound to surfaces of particles suspended in water or present in soil, e.g. hydrous ferric oxides (HFO). It is to be expected that speciation and solid-liquid distribution of iodine strongly depends on environmental conditions. In this study, the speciation and solid-liquid distribution of iodine in environmental samples such as waste water, sewage sludge and soil are estimated with the help of the geochemical code PHREEQC. The calculations are carried out using chemical equilibrium and sorption data from the literature and chemical analyses of the media. We present the results of these calculations and compare them with experimental results of medical {sup 131}I in waste water and sewage sludge. The output of this study will be used in future work where transport and distribution of iodine in wastewater treatment plants and in irrigated agricultural soils will be modeled. (authors)

  2. Recent advances in on-line coupling of capillary electrophoresis to atomic absorption and fluorescence spectrometry for speciation analysis and studies of metal-biomolecule interactions

    International Nuclear Information System (INIS)

    Li Yan; Yin Xuebo; Yan Xiuping

    2008-01-01

    Speciation information is vital for the understanding of the toxicity, mobility and bioavailability of elements in environmental or biological samples. Hyphenating high resolving power of separation techniques and element-selective detectors provides powerful tools for studying speciation of trace elements in environmental and biological systems. During the last five years several novel hybrid techniques based on capillary electrophoresis (CE) and atomic spectrometry have been developed for speciation analysis and metal-biomolecule interaction study in our laboratory. These techniques include CE on-line coupled with atomic fluorescence spectrometry (AFS), chip-CE on-line coupled with AFS, CE on-line coupled with flame heated quartz furnace atomic absorption spectrometry (FHF-AAS), and CE on-line coupled with electrothermal atomic absorption spectrometry (ETAAS). The necessity for the development of these techniques, their interface design, and applications in speciation analysis and metal-biomolecule interaction study are reviewed. The advantages and limitations of the developed hybrid techniques are critically discussed, and further development is also prospected

  3. Genomics of Rapid Incipient Speciation in Sympatric Threespine Stickleback.

    Directory of Open Access Journals (Sweden)

    David A Marques

    2016-02-01

    Full Text Available 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.

  4. Pollinator-Driven Speciation in Sexually Deceptive Orchids

    Directory of Open Access Journals (Sweden)

    Shuqing Xu

    2012-01-01

    Full Text Available Pollinator-mediated selection has been suggested to play a major role for the origin and maintenance of the species diversity in orchids. Sexually deceptive orchids are one of the prime examples for rapid, pollinator-mediated plant radiations, with many species showing little genetic differentiation, lack of postzygotic barriers, but strong prezygotic reproductive isolation. These orchids mimic mating signals of female insects and employ male insects as pollinators. This kind of sexual mimicry leads to highly specialised pollination and provides a good system for investigating the process of pollinator-driven speciation. Here, we summarise the knowledge of key processes of speciation in this group of orchids and conduct a meta-analysis on traits that contribute to species differentiation, and thus potentially to speciation. Our study suggests that pollinator shift through changes in floral scent is predominant among closely related species in sexually deceptive orchids. Such shifts can provide a mechanism for pollinator-driven speciation in plants, if the resulting floral isolation is strong. Furthermore, changes in floral scent in these orchids are likely controlled by few genes. Together these factors suggest speciation in sexually deceptive orchids may happen rapidly and even in sympatry, which may explain the remarkable species diversity observed in this plant group.

  5. Speciation and Health Risks of Atmospheric Nanoparticulates

    Science.gov (United States)

    Nguyen, Kennedy

    Exposure to air pollution causes several adverse health effects such as asthma, respiratory disease, cardiovascular disease, cancer, and premature death; and the San Joaquin Valley is one of the most heavily polluted regions in the US. The mountains that surround the valley allow air pollution, including particulate matter, to remain stagnant, prolonging the exposure of valley populations to it. The primary sources of particulate matter for this region are aluminosilicate dust from agricultural activities, and soot emissions from diesel trucks and vehicular traffic. A substantial fraction of emitted material is nanoparticulate matter (testing in cell culture studies, and correlation of particulate properties and sources with their negative health impacts. These results can help identify the sources of air pollution to prioritize for mitigation for the greatest health benefit. In addition, further chemical speciation can help monitor the results of such mitigation efforts. Here, natural particulate matter samples from Merced and Fresno, two cities in the San Joaquin Valley, were analyzed. Ultrafine particles present were 40 to 50 nm in diameter and mostly composed of aluminum, silicon, oxygen, and iron hydroxide. XAS data confirmed the presence of the aluminosilicate as smectite clay and the iron hydroxide as ferrihydrite. Furthermore, a chemical speciation study investigated industrial emissions of air particulate matter. Samples were analyzed using electron microscopy for elemental composition and size distribution, and found to contain fine metal particulates (lead and iron) that can lead to lung inflammation. From characterization data, in order to create a simplified proxy particle system for cell culture studies, amorphous silica particles were synthesized using a modified Stober Synthesis and coated with iron hydroxide. A range of iron hydroxide concentrations (0.06 to 1.63 mmol of iron per gram of silica) were used to test the effect of iron contamination on

  6. Voltammetric Investigation Of Hydrothermal Iron Speciation

    Directory of Open Access Journals (Sweden)

    Charlotte eKleint

    2016-05-01

    Full Text Available Hydrothermal vent fluids are highly enriched in iron (Fe compared to ambient seawater, and organic ligands may play a role in facilitating the transport of some hydrothermal Fe into the open ocean. This is important since Fe is a limiting micronutrient for primary production in large parts of the world`s surface ocean. We have investigated the concentration and speciation of Fe in several vent fluid and plume samples from the Nifonea vent field, Coriolis Troughs, New Hebrides Island Arc, South Pacific Ocean using competitive ligand exchange - adsorptive cathodic stripping voltammetry (CLE - AdCSV with salicylaldoxime (SA as the artificial ligand. Our results for total dissolved Fe (dFe in the buoyant hydrothermal plume samples showed concentrations up to 3.86 µM dFe with only a small fraction between 1.1% and 11.8% being chemically labile. Iron binding ligand concentrations ([L] were found in µM level with strong conditional stability constants up to log K[L],Fe3+ of 22.9. Within the non-buoyant hydrothermal plume above the Nifonea vent field, up to 84.7% of the available Fe is chemically labile and [L] concentrations up to 97 nM were measured. [L] was consistently in excess of Felab, indicating that all available Fe is being complexed, which in combination with high Felab values in the non-buoyant plume, signifies that a high fraction of hydrothermal dFe is potentially being transported away from the plume into the surrounding waters, contributing to the global oceanic Fe budget.

  7. Microimaging and tomography with chemical speciation

    Energy Technology Data Exchange (ETDEWEB)

    Rau, C. E-mail: rau@esrf.fr; Somogyi, A.; Simionovici, A

    2003-01-01

    Materials science deals with the study of the morphology of samples, their chemical composition and the relation between both. One general problem is the preservation of the sample throughout the different analyses, like it is often the case for classical chemical analysis. Destruction-free chemical speciation in three dimensions with micrometer resolution can be achieved by combining X-ray spectroscopy and imaging techniques. Highly brilliant radiation is needed for this purpose available at 3rd generation synchrotrons such as the ESRF. X-ray absorption near-edge spectroscopy (XANES) is a non-destructive well-known and established technique in chemistry. By scanning the X-ray energy in the vicinity (50-100 eV) of the absorption edge of an element, information can be obtained about the oxidation state of the probed atoms. The (conventional) technique mainly employed until now applies to homogeneous, specifically prepared flat samples where the measured signal can be considered as the average over the whole irradiated volume. This restriction for samples is partially released when the XANES method is combined with imaging techniques. 2D resolved data is acquired using area detectors or by scanning with a focussed beam. X-ray absorption tomography is a method of choice for investigating the 3D structure of objects and its dual energy version is used for getting information about the 3D distribution of a given element within the sample. Although the combination of XANES and tomography seems to be a natural extension of dual-energy tomography, in practice several experimental problems have to be overcome in order to obtain useable data. In the following we describe the results of XANES imaging and tomography obtained measuring a phantom sample of pure molybdenum compounds using a FreLoN 2000 camera system at the ESRF undulator beamline ID22. This system allowed making volume resolved distinctions between different oxidation states with spatial resolution in the

  8. Applicability of multisyringe chromatography coupled to cold-vapor atomic fluorescence spectrometry for mercury speciation analysis

    International Nuclear Information System (INIS)

    Guzmán-Mar, J.L.; Hinojosa-Reyes, L.; Serra, A.M.; Hernández-Ramírez, A.; Cerdà, V.

    2011-01-01

    Graphical abstract: An automatic system, based on the applicability of multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) detection is developed for mercury speciation. Highlights: ► The on-line coupling of MSC to CV/AFS was developed for mercury speciation analysis. ► The speciation of MeHg + , Hg 2+ and EtHg + was achieved on a RP C18 monolithic column. ► The hyphenated system provided higher sample throughput compared to HPLC–CV/AFS. ► The limits of detection for mercury species were comparable or better than those reported by HPLC–CV/AFS. ► The developed method also provided low instrumental and operational costs. - Abstract: In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg 2+ ), methylmercury (MeHg + ) and ethylmercury (EtHg + ) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)–acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)–acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3σ) were found to be 0.03, 0.11 and 0.09 μg L −1 for MeHg + , Hg 2+ and EtHg + , respectively. The relative standard deviation (RSD, n = 6) of the peak height for 3, 6 and 3 μg L −1 of MeHg + , Hg 2+ and EtHg + (as Hg) ranged from 2.4 to 4.0%. Compared with the conventional HPLC–CV/AFS hyphenated systems

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-15

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

  10. [Influence of Dissimilatory Iron Reduction on the Speciation and Bioavailability of Heavy Metals in Soil].

    Science.gov (United States)

    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.

  11. Real-Time Speciation of Uranium During Active Bioremediation and U(IV) Reoxidation

    International Nuclear Information System (INIS)

    Komlos, J.; Mishra, B.; Lanzirotti, A.; Myneni, S.; Jaffe, P.

    2008-01-01

    The biological reduction of uranium from soluble U(VI) to insoluble U(IV) has shown potential to prevent uranium migration in groundwater. To gain insight into the extent of uranium reduction that can occur during biostimulation and to what degree U(IV) reoxidation will occur under field relevant conditions after biostimulation is terminated, X-ray absorption near edge structure (XANES) spectroscopy was used to monitor: (1) uranium speciation in situ in a flowing column while active reduction was occurring; and (2) in situ postbiostimulation uranium stability and speciation when exposed to incoming oxic water. Results show that after 70 days of bioreduction in a high (30 mM) bicarbonate solution, the majority (>90%) of the uranium in the column was immobilized as U(IV). After acetate addition was terminated and oxic water entered the column, in situ real-time XANES analysis showed that U(IV) reoxidation to U(VI) (and subsequent remobilization) occurred rapidly (on the order of minutes) within the reach of the oxygen front and the spatial and temporal XANES spectra captured during reoxidation allowed for real-time uranium reoxidation rates to be calculated.

  12. Speciation analysis of cobalt in foods by high-performance liquid chromatography and neutron activation analysis

    International Nuclear Information System (INIS)

    Muto, Toshio; Koyama, Motoko

    1994-01-01

    A combined method by coupling high-performance liquid chromatography (HPLC, as a separation method) with neutron activation analysis (as a detection method) have been applied to the speciation analysis of cobalt in daily foods (e.g. egg, fish and milk). Cobalt species including free cobalt, vitamin B 12 and protein-bound cobalt were separated with a preparative HPLC and a centrifuge. Subsequently, the determination of cobalt in the separated species was made by neutron activation analysis. The results showed that the content of the total cobalt in the foods was found to lie in the range 0.4-11ng/g(0.4-11ppb) based on wet weight. The compositions of free cobalt, vitamin B 12 and protein-bound cobalt were ranged 16-43%, 55-73%, 2.3-17%, respectively. These experimental evidences suggest that the combination of HPLC and neutron activation analysis is expected to be a useful tool for speciation analysis of trace elements in biological as well as environmental materials. (author)

  13. Genomic Signatures of Speciation in Sympatric and Allopatric Hawaiian Picture-Winged Drosophila.

    Science.gov (United States)

    Kang, Lin; Settlage, Robert; McMahon, Wyatt; Michalak, Katarzyna; Tae, Hongseok; Garner, Harold R; Stacy, Elizabeth A; Price, Donald K; Michalak, Pawel

    2016-05-30

    The Hawaiian archipelago provides a natural arena for understanding adaptive radiation and speciation. The Hawaiian Drosophila are one of the most diverse endemic groups in Hawaiì with up to 1,000 species. We sequenced and analyzed entire genomes of recently diverged species of Hawaiian picture-winged Drosophila, Drosophila silvestris and Drosophila heteroneura from Hawaiì Island, in comparison with Drosophila planitibia, their sister species from Maui, a neighboring island where a common ancestor of all three had likely occurred. Genome-wide single nucleotide polymorphism patterns suggest the more recent origin of D. silvestris and D. heteroneura, as well as a pervasive influence of positive selection on divergence of the three species, with the signatures of positive selection more prominent in sympatry than allopatry. Positively selected genes were significantly enriched for functional terms related to sensory detection and mating, suggesting that sexual selection played an important role in speciation of these species. In particular, sequence variation in Olfactory receptor and Gustatory receptor genes seems to play a major role in adaptive radiation in Hawaiian pictured-winged Drosophila. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

  14. Speciation of protein-bound trace elements by gel electrophoresis and atomic spectrometry.

    Science.gov (United States)

    Ma, Renli; McLeod, Cameron W; Tomlinson, Kerry; Poole, Robert K

    2004-08-01

    The metabolism of trace elements, in particular their binding to proteins in biological systems is of great importance in biochemical, toxicological, and pharmacological studies. As a result there has been a sustained interest over the last two decades in the speciation of protein-bound metals. Various analytical approaches have been employed, combining efficient separation of metalloproteins by liquid chromatography or electrophoresis with high-sensitivity elemental detection. Slab-gel electrophoresis (GE) is a key platform for high-resolution protein separation, and has been combined with autoradiography and various atomic spectrometric techniques for in-gel determination of protein-bound metals. Recently, the combination of GE with state-of-the-art inductively coupled plasma-mass spectrometry (ICP-MS), particularly when linked to laser ablation (LA) for direct gel interrogation, has opened up new opportunities for rapid characterization of metalloproteins. The use of GE and atomic spectrometry for the speciation of protein-bound trace elements is reviewed in this paper. Technical requirements for gel electrophoresis/atomic spectrometric measurement are considered in terms of method compatibilities, detection capability and potential usefulness. The literature is also surveyed to illustrate current status and future trends. Copyright 2004 Wiley-VCH Verlag GmbH and Co.

  15. Simultaneous speciation of trace elements using chemical separation and neutron activation

    International Nuclear Information System (INIS)

    Chatt, A.

    2003-01-01

    Speciation neutron activation analysis (SNAA) is a sophisticated analytical technique which can be developed for studying the simultaneous speciation of a number of elements in a variety of matrices. The advantages of SNAA are demonstrated with typical examples such as (i) arsenic speciation in sea foods and water, and simultaneous speciation of (ii) arsenic, antimony and selenium in water, (iii) chlorine, bromine and iodine in fish, (iv) lanthanides in simulated vitrified waste, and (v) trace elements bound to proteins. (author)

  16. Patterns of plant speciation in the Cape floristic region.

    Science.gov (United States)

    van der Niet, Timotheüs; Johnson, Steven D

    2009-04-01

    Plant species have accumulated in the Cape region of southern Africa to a much greater degree than in areas of equivalent size in the rest of the subcontinent. Although this could be a consequence simply of lower extinction rates in the Cape, most researchers have invoked high rates of ecological speciation, driven by unique aspects of the Cape environment, as the primary explanation for this richness. To assess these ideas, we analyzed the frequencies of ecological shifts among 188 sister species pairs obtained from molecular phylogenies of eight Cape clades. Ecological shifts were evident in 80% of sister species pairs, with general habitat, pollinator, and fire-survival strategy shifts being especially frequent. Contrary to an established idea that shifts in soil type are frequently associated with speciation of Cape taxa, these shifts were relatively rare, occurring in just 17% of species pairs. More cases of sister species divergence are accompanied solely by floral than by vegetative diversification, suggesting an important role for pollinator-driven speciation. In an analysis of two large orchid genera that have radiated in both the Cape and the rest of southern Africa, the frequency of ecological shifts (general habitat, soil type, altitude and flowering time), did not differ between sister species pairs in the Cape region and those outside it. Despite suggestions that Cape plants tend to have small range sizes and show fine-scale patterns of speciation, range size did not differ significantly between species in the Cape and those outside it. We conclude that ecological speciation is likely to have been important for radiation of the Cape flora, but there is no evidence as yet for special "Cape" patterns of ecological speciation.

  17. Towards accounting for dissolved iron speciation in global ocean models

    Directory of Open Access Journals (Sweden)

    A. Tagliabue

    2011-10-01

    Full Text Available The trace metal iron (Fe is now routinely included in state-of-the-art ocean general circulation and biogeochemistry models (OGCBMs because of its key role as a limiting nutrient in regions of the world ocean important for carbon cycling and air-sea CO2 exchange. However, the complexities of the seawater Fe cycle, which impact its speciation and bioavailability, are simplified in such OGCBMs due to gaps in understanding and to avoid high computational costs. In a similar fashion to inorganic carbon speciation, we outline a means by which the complex speciation of Fe can be included in global OGCBMs in a reasonably cost-effective manner. We construct an Fe speciation model based on hypothesised relationships between rate constants and environmental variables (temperature, light, oxygen, pH, salinity and assumptions regarding the binding strengths of Fe complexing organic ligands and test hypotheses regarding their distributions. As a result, we find that the global distribution of different Fe species is tightly controlled by spatio-temporal environmental variability and the distribution of Fe binding ligands. Impacts on bioavailable Fe are highly sensitive to assumptions regarding which Fe species are bioavailable and how those species vary in space and time. When forced by representations of future ocean circulation and climate we find large changes to the speciation of Fe governed by pH mediated changes to redox kinetics. We speculate that these changes may exert selective pressure on phytoplankton Fe uptake strategies in the future ocean. In future work, more information on the sources and sinks of ocean Fe ligands, their bioavailability, the cycling of colloidal Fe species and kinetics of Fe-surface coordination reactions would be invaluable. We hope our modeling approach can provide a means by which new observations of Fe speciation can be tested against hypotheses of the processes present in governing the ocean Fe cycle in an

  18. Variation in Linked Selection and Recombination Drive Genomic Divergence during Allopatric Speciation of European and American Aspens.

    Science.gov (United States)

    Wang, Jing; Street, Nathaniel R; Scofield, Douglas G; Ingvarsson, Pär K

    2016-07-01

    Despite the global economic and ecological importance of forest trees, the genomic basis of differential adaptation and speciation in tree species is still poorly understood. Populus tremula and Populus tremuloides are two of the most widespread tree species in the Northern Hemisphere. Using whole-genome re-sequencing data of 24 P. tremula and 22 P. tremuloides individuals, we find that the two species diverged ∼2.2-3.1 million years ago, coinciding with the severing of the Bering land bridge and the onset of dramatic climatic oscillations during the Pleistocene. Both species have experienced substantial population expansions following long-term declines after species divergence. We detect widespread and heterogeneous genomic differentiation between species, and in accordance with the expectation of allopatric speciation, coalescent simulations suggest that neutral evolutionary processes can account for most of the observed patterns of genetic differentiation. However, there is an excess of regions exhibiting extreme differentiation relative to those expected under demographic simulations, which is indicative of the action of natural selection. Overall genetic differentiation is negatively associated with recombination rate in both species, providing strong support for a role of linked selection in generating the heterogeneous genomic landscape of differentiation between species. Finally, we identify a number of candidate regions and genes that may have been subject to positive and/or balancing selection during the speciation process. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

  19. The EU network on trace element speciation in full swing

    DEFF Research Database (Denmark)

    Cornelis, R.; Camara, C.; Ebdon, L.

    2000-01-01

    health and hygiene. The network covers a number of important issues including organotin compounds, chromium and nickel species, chemical characterisation of environmental and industrial particulate samples, risk assessment, selenium and a series of other essential and toxic elements in food, as well......The EC-funded thematic network 'Speciation 21' links scientists in analytical chemistry working in method development for the chemical speciation of trace elements, and potential users from industry and representatives of legislative agencies, in the field of environment, food and occupational...

  20. Speciation of Long-Lived Radionuclides in the Environment

    DEFF Research Database (Denmark)

    Hou, Xiaolin

    , isotopes of Pu, and 237Np in seawater, fresh water, soil, sediment, vegetations, and concrete. The developed methods are used for the investigation of the chemical speciation of these radionuclides as well as their environmental behaviours, especially in Danish environment. In addition the speciation of Pu...... isotopes in waste samples from the decommissioning of Danish nuclear facilities is also investigated. The report summarizes these works completed in this project. Through this research project, a number of research papers have been published in the scientific journals, the research results has also been...

  1. Assessing models of speciation under different biogeographic scenarios; An empirical study using multi-locus and RNA-seq analyses

    Science.gov (United States)

    Edwards, Taylor; Tollis, Marc; Hsieh, PingHsun; Gutenkunst, Ryan N.; Liu, Zhen; Kusumi, Kenro; Culver, Melanie; Murphy, Robert W.

    2016-01-01

    Evolutionary biology often seeks to decipher the drivers of speciation, and much debate persists over the relative importance of isolation and gene flow in the formation of new species. Genetic studies of closely related species can assess if gene flow was present during speciation, because signatures of past introgression often persist in the genome. We test hypotheses on which mechanisms of speciation drove diversity among three distinct lineages of desert tortoise in the genus Gopherus. These lineages offer a powerful system to study speciation, because different biogeographic patterns (physical vs. ecological segregation) are observed at opposing ends of their distributions. We use 82 samples collected from 38 sites, representing the entire species' distribution and generate sequence data for mtDNA and four nuclear loci. A multilocus phylogenetic analysis in *BEAST estimates the species tree. RNA-seq data yield 20,126 synonymous variants from 7665 contigs from two individuals of each of the three lineages. Analyses of these data using the demographic inference package ∂a∂i serve to test the null hypothesis of no gene flow during divergence. The best-fit demographic model for the three taxa is concordant with the *BEAST species tree, and the ∂a∂i analysis does not indicate gene flow among any of the three lineages during their divergence. These analyses suggest that divergence among the lineages occurred in the absence of gene flow and in this scenario the genetic signature of ecological isolation (parapatric model) cannot be differentiated from geographic isolation (allopatric model).

  2. Neptunium speciation (complexation and redox behaviour) in aqueous citrate medium

    International Nuclear Information System (INIS)

    Bonin, L.; Ansoborlo, E.; Moisy, Ph.

    2005-01-01

    Full text of publication follows: In the framework of the French Environmental Nuclear Toxicology programme, additional experiments related to the decorporation of actinides are planned. The lack of information on the neptunium behaviour within blood and the inefficiency of therapeutic treatments, led us to study the complexation of this element with basic anions. Within this purpose, the in vitro behaviour of Np IV and Np V in simple media simulating biological media was studied: blood plasma is one of the media of interest and it can be simulated, from a chemical point of view, by an aqueous solution with pH 7.4, containing ions such as citrate (1.6 10 -4 mol/L), lactate (1.5 10 -3 mol/L), CO 3 2- (2.5 10 -2 mol/L), PO 4 3- (1.1 10 -3 mol/L), SO 4 2- (3.3 10 -4 mol/L) and Cl - (9 10 -2 mol/L). This study was more specifically focused on the behaviour of neptunium with citrate ion, which is also a basic ligand to consider when one wishes to study the migration of actinides in the environment, since it exists in significant amounts in the ground due to its production by the plants. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np V with various acid-basic forms of the citrate anion was observed; regarding Np IV , two complexes, with 1:1 and 1:2 stoichiometry, have been respectively observed. The reactivity of Np VI is probably similar to the behaviour of U VI , which is reported in literature to form a complex with a 1:1 stoichiometry with the Cit 3- anion From the quantitative study of these equilibria, it has been possible to determine the values of various equilibrium constants. Concerning the stability of neptunium towards oxido-reduction, it was confirmed that Np VI was very quickly reduced to Np V by the citrate anions, whereas Np IV was stable. In the case of Np V , it was observed that, depending on the pH and the citrate

  3. Early events in speciation: polymorphism for hybrid male sterility in Drosophila.

    Science.gov (United States)

    Reed, Laura K; Markow, Therese A

    2004-06-15

    Capturing the process of speciation early enough to determine the initial genetic causes of reproductive isolation remains a major challenge in evolutionary biology. We have found, to our knowledge, the first example of substantial intraspecific polymorphism for genetic factors contributing to hybrid male sterility. Specifically, we show that the occurrence of hybrid male sterility in crosses between Drosophila mojavensis and its sister species, Drosophila arizonae, is controlled by factors present at different frequencies in different populations of D. mojavensis. In addition, we show that hybrid male sterility is a complex phenotype; some hybrid males with motile sperm still cannot sire offspring. Because male sterility factors in hybrids between these species are not yet fixed within D. mojavensis, this system provides an invaluable opportunity to characterize the genetics of reproductive isolation at an early stage.

  4. Electrochemical metal speciation in natural and model polyelectrolyte systems

    NARCIS (Netherlands)

    Hoop, van den M.A.G.T.

    1994-01-01

    The purpose of the research described in this thesis was to examine the applicability of electro-analytical techniques in obtaining information on the speciation of metals, i.e. their distribution over different physico-chemical forms, in aquatic systems containing charged macromolecules.

  5. Speciation and determination of priority metals in sediments of Oyun ...

    African Journals Online (AJOL)

    This work was carried out to determine the concentrations, bioavailability and mobility of priority metals in sediments of Oyun River, Sango, Ilorin, Nigeria. The river sediments were sampled at six selected locations and the samples were analyzed for some certain priority metals to determine the concentration, speciation and ...

  6. Speciation and phase separation of water in quartz (A review ...

    African Journals Online (AJOL)

    By sp3-hybridization of electron bonds, the water molecule exhibits a tetrahedral charged structure, leading to various water point defects in the form of substitution of ... The formation of combined defect [SiO4]-H2O-M+ [M3+O4] upon water speciation (M+ is metallic ion), is an indication of the presence of hydrous species.

  7. Heavy metal speciation and their accumulation in sediments of Lake ...

    African Journals Online (AJOL)

    UFUOMA

    Key words: Heavy metals, chemical speciation, sediments, Burullus, Lake. INTRODUCTION ..... fuel for use in internal combustion engines and in making batteries. ..... (Tuner, 1989). According to this model, human risk assessment was .... 593 - 594. Hökanson L (1980). "Ecological Risk Index for Aquatic Pollution. Control.

  8. Comparative Studies of the Speciation Patterns of Nickel and ...

    African Journals Online (AJOL)

    Results of speciation stdies of nickel and chromium in wastewater, surface and groundwater systems using flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectrometry (GFAAS) and differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV) are presented. Dimethylglyoxime ...

  9. Fractionation, characterization and speciation of heavy metals in ...

    African Journals Online (AJOL)

    Speciation of heavy metals in soils determines the availability for metals for plant uptake and potential for contamination of groundwater following application of composts to agricultural lands. Methods used to characterize heavy metals in solid phase of composts and compost amended soils include physical fractionation ...

  10. Behavioural isolation may facilitate homoploid hybrid speciation in cichlid fish

    NARCIS (Netherlands)

    Selz, O. M.; Thommen, R.; Maan, M. E.; Seehausen, O.

    Hybrid speciation is constrained by the homogenizing effects of gene flow from the parental species. In the absence of post-mating isolation due to structural changes in the genome, or temporal or spatial premating isolation, another form of reproductive isolation would be needed for homoploid

  11. The molecular basis of speciation: from patterns to processes, rules ...

    Indian Academy of Sciences (India)

    male; large X-effect; meiotic drive; genomic conflict. Abstract. The empirical study of speciation has brought us closer to unlocking the origins of life's vast diversity. By examining recently formed species, a number of general patterns, or rules, ...

  12. Heavy metal speciation and their accumulation in sediments of Lake ...

    African Journals Online (AJOL)

    Several sediment samples in Lake Burullus have been affected by the discharges of heavy metals through different drains. The study aimed to analyze the chemical speciation of these metals. In particular, the chemical forms of Cd, Cu, Fe, Mn, Pb and Zn in sediments collected in spring season were studied using a ...

  13. Geometry, charge distribution, and surface speciation of phosphate on goethite.

    NARCIS (Netherlands)

    Rahnemaie, R.; Hiemstra, T.; Riemsdijk, van W.H.

    2007-01-01

    The surface speciation of phosphate has been evaluated with surface complexation modeling using an interfacial charge distribution (CD) approach based on ion adsorption and ordering of interfacial water. In the CD model, the charge of adsorbed ions is distributed over two electrostatic potentials in

  14. Speciation of Fe in Fe-modified zeolite catalysts

    Czech Academy of Sciences Publication Activity Database

    Smoláková, L.; Grygar, Tomáš; Čapek, L.; Schneeweiss, Oldřich; Zbořil, R.

    2010-01-01

    Roč. 647, č. 1 (2010), s. 8-19 ISSN 1572-6657 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z20410507 Keywords : solid state speciation * Fe2O3 * heterogeneous catalysts Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.732, year: 2010

  15. Speciation Studies of Some Toxic Metal Complexes of Glycylglycine ...

    African Journals Online (AJOL)

    NICO

    mixtures apart from its established utility in understanding ... Chemical speciation of metals is important for an understand- ... Titrations with differ- ent ratios (1:2.5, 1:3.5 and 1:5) of metal-ligand were performed with 0.4 mol L–1 sodium hydroxide solution. The mixtures obtained from PG and water are non-ideal due.

  16. Speciation of Candida isolates obtained from diarrheal stool

    Directory of Open Access Journals (Sweden)

    Beena Uppal

    2016-01-01

    Conclusion Candida diarrhea was mostly seen in individuals younger than 12 years, most commonly caused by C. krusei. Resistance to fluconazole was high. A rising resistance to amphotericin B is alarming. Speciation of Candida is important to see the difference in antifungal susceptibility in different species.

  17. FINE PARTICULATE MATTER (PM) AND ORGANIC SPECIATION OF FIREPLACE EMISSIONS

    Science.gov (United States)

    This paper presents a summary of fireplace particle size and organic speciation data gathered to date in an on-going project. Tests are being conducted in a residential wood combustion (RWC) laboratory on three factory-built fireplaces. RWC wood smoke particles <10?m (PM10) con...

  18. Speciation of Zinc Mixed Ligand Complexes in Salt Water Systems ...

    African Journals Online (AJOL)

    Speciation of Zinc Mixed Ligand Complexes in Salt Water Systems. ... method has been used to study heavy metal interaction in model lake water in KNO3 ... is of no consequential effect because in its normal state, the [OH-] of the lake water is ...

  19. Speciation and bioavailability of copper in Lake Tjeukemeer

    NARCIS (Netherlands)

    Verweij, W.

    1991-01-01

    Chapter 1: introduction

    In this thesis an account is given of a research project dealing with the chemical speciation and bioavailability of copper in Lake Tjeukemeer, a lake in the north of the Netherlands. The reason for the initiation of this project was a lack of

  20. Distribution and Speciation of Mercury in Mine Waste Dumps

    Czech Academy of Sciences Publication Activity Database

    Hojdová, Maria; Navrátil, Tomáš; Rohovec, Jan

    2008-01-01

    Roč. 80, č. 3 (2008), s. 237-241 ISSN 0007-4861 R&D Projects: GA AV ČR(CZ) KJB300130615 Institutional research plan: CEZ:AV0Z30130516 Keywords : mercury * mine waste * mercury speciation * thermo-desorption analysis Subject RIV: DD - Geochemistry Impact factor: 0.609, year: 2008

  1. Speciation and migration of 129I in soil profiles

    DEFF Research Database (Denmark)

    Luo, Maoyi; Hou, Xiaolin; Zhou, Weijian

    2013-01-01

    A method has been developed for speciation analysis of ultra low level 129I in soil using sequential extraction combined with coprecipitation for separation of carrier free iodine and AMS measurement of 129I. Two loess profiles collected from northwest China were analyzed for species of 129I...

  2. Phytotoxicity and bioavailablity of nickel: chemical speciation and bioaccumulation

    NARCIS (Netherlands)

    Weng, L.P.; Lexmond, T.M.; Wolthoorn, A.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2003-01-01

    The effect of pH on the bioaccumulation of nickel (Ni) by plants is opposite when using a nutrient solution or a soil as a growing medium. This paradox can be understood if the pH effect on the bioaccumulation, on the chemical speciation in the soil solution, and on the binding to the soil of Ni are

  3. Speciation of trace elements in the environmental studies

    International Nuclear Information System (INIS)

    Reddy, A.V.R.

    2012-01-01

    Elements present at trace levels, often referred as trace elements, play an important role in the environment and in the functioning of life on our planet. Trace elements in environment present as free metal ions or incorporated into colloids or attached to particulate matter or exist in different physical and chemical forms. It is well established that some elements are highly toxic and some are essential, but can become toxic at higher doses. It is also now known that the forms of elements (speciation) and their amounts are more important than the chemical dose of the elements as their interaction depends on different species. For example, Cr(VI) ions are considered far more toxic than Cr(III), whereas As(III) is more toxic than As(V). Similarly, in the case of mercury, both methylmercury and inorganic mercury are toxic but they show different levels of toxicity. Thus the adverse effects depend on the nature of species of the elements and therefore speciation studies are of paramount importance in many areas like toxicology, environmental chemistry and geochemisty. In view of this, speciation studies is a challenge to analytical chemists as the measurement methodologies have to be carefully developed, validated and applied. The grand challenge is to obtain quality data ensuring traceability, as the data obtained will be used in modeling for predicting the environmental impacts. In this talk importance of speciation and challenges to environmental analytical chemists will be discussed along with the following three speciation studies on Cr, U and Hg which were carried out in our laboratories

  4. Purex process modelling - do we really need speciation data?

    International Nuclear Information System (INIS)

    Taylor, R.J.; May, I.

    2001-01-01

    The design of reprocessing flowsheets has become a complex process requiring sophisticated simulation models, containing both chemical and engineering features. Probably the most basic chemical data needed is the distribution of process species between solvent and aqueous phases at equilibrium, which is described by mathematical algorithms. These algorithms have been constructed from experimentally determined distribution coefficients over a wide range of conditions. Distribution algorithms can either be empirical fits of the data or semi-empirical equations, which describe extraction as functions of process variables such as temperature, activity coefficients, uranium loading, etc. Speciation data is not strictly needed in the accumulation of distribution coefficients, which are simple ratios of analyte concentration in the solvent phase to that in the aqueous phase. However, as we construct process models of increasing complexity, speciation data becomes much more important both to raise confidence in the model and to understand the process chemistry at a more fundamental level. UV/vis/NIR spectrophotometry has been our most commonly used speciation method since it is a well-established method for the analysis of actinide ion oxidation states in solution at typical process concentrations. However, with the increasing availability to actinide science of more sophisticated techniques (e.g. NMR; EXAFS) complementary structural information can often be obtained. This paper will, through examples, show how we have used spectrophotometry as a primary tool in distribution and kinetic experiments to obtain data for process models, which are then validated through counter-current flowsheet trials. It will also discuss how spectrophotometry and other speciation methods are allowing us to study the link between molecular structure and extraction behaviour, showing how speciation data really is important in PUREX process modelling. (authors)

  5. Sex chromosomes and speciation in birds and other ZW systems.

    Science.gov (United States)

    Irwin, Darren E

    2018-02-14

    Theory and empirical patterns suggest a disproportionate role for sex chromosomes in evolution and speciation. Focusing on ZW sex determination (females ZW, males ZZ; the system in birds, many snakes, and lepidopterans), I review how evolutionary dynamics are expected to differ between the Z, W and the autosomes, discuss how these differences may lead to a greater role of the sex chromosomes in speciation and use data from birds to compare relative evolutionary rates of sex chromosomes and autosomes. Neutral mutations, partially or completely recessive beneficial mutations, and deleterious mutations under many conditions are expected to accumulate faster on the Z than on autosomes. Sexually antagonistic polymorphisms are expected to arise on the Z, raising the possibility of the spread of preference alleles. The faster accumulation of many types of mutations and the potential for complex evolutionary dynamics of sexually antagonistic traits and preferences contribute to a role for the Z chromosome in speciation. A quantitative comparison among a wide variety of bird species shows that the Z tends to have less within-population diversity and greater between-species differentiation than the autosomes, likely due to both adaptive evolution and a greater rate of fixation of deleterious alleles. The W chromosome also shows strong potential to be involved in speciation, in part because of its co-inheritance with the mitochondrial genome. While theory and empirical evidence suggest a disproportionate role for sex chromosomes in speciation, the importance of sex chromosomes is moderated by their small size compared to the whole genome. © 2018 John Wiley & Sons Ltd.

  6. Simultaneous speciation neutron activation analysis for trace elements

    International Nuclear Information System (INIS)

    Chatt, A.; Kiceniuk, J.W.; Menendez Sanchez, W.; Bottaro, C.

    2006-01-01

    Among the various forms of neutron activation technique being developed in our laboratory, much emphasis has been placed over the last ten years or so on the development of simultaneous speciation neutron activation analysis (SSNAA). This technique can now be used for the simultaneous determination of various species of a number of elements. Almost all speciation techniques consist of two steps. The first step involves the separation of species from the sample followed by the second step of element-specific detection. A number of characteristic features of NAA, which other techniques normally do not possess, can be advantageously exploited in SSNAA. For example, SSNAA can be used for: (i) multielement speciation with high specificity, (ii) speciation of chemically dissimilar elements such as Cd, Mn and Se, (iii) speciation of elements such as Cl, Br and I which are rather difficult to determine by most other techniques, etc. We have developed SSNAA methods for assaying various arsenic species, namely As(III), As(V), dimethyl arsonic acid (DMA), monomethylarsinic acid (MMA), arsenobetaine (AsB), organically bound arsenic (OBAs), and lipid-soluble arsenic (LSAs) in marine fish samples. We have extended these methods to include simultaneous determination of various species of As, Sb and Se in water. We have also developed SSNAA methods employing biochemical techniques for the simultaneous separation, preconcentration and characterization of metalloproteins and protein-bound trace element species of As, Br, Cd, Cu, Mn, Se, and Zn. We have developed methods for the simultaneous separation and characterization of organohalogen compounds in fish. An overview of the SSNAA methods being developed in our laboratory will be presented. (author)

  7. Speciation analysis of arsenic compounds in the serum and urine of a patient with acute arsine poisoning

    Directory of Open Access Journals (Sweden)

    Yamanaka K.

    2013-04-01

    Full Text Available Arsine is one of the most potent hemolytic agents. It is important to clarify arsine metabolism as well as its chemical interactions with biological components. The aim of the present study was to clarify arsine metabolism by arsenic speciation analysis in serum and urine from an acute poisoning patient with hematuria, anemia, and renal and liver dysfunction. Speciation analysis of arsenics in serum and urine was performed using HPLC-ICP-MS. The total arsenic (T-As concentration in serum was 244.8 μg/l at admission and 97.1 μg/l at discharge. In the speciation analysis, four kinds of As compounds derived from arsine metabolism were detected in serum and urine. The concentration of arsenite (AsIII, arsenate (AsV, monomethylarsonic acid (MMA, and dimethylarsinic acid (DMA in serum at admission were 45.8, 5.2, 17.9 and 9.3 μg/l, respectively. The concentrations of AsIII, AsV, and MMA decreased with biological half time (BHT of 30.1, 43.0, and 96.3 h, respectively. Only DMA was increased at discharge. The urinary AsIII, AsV, MMA and DMA concentrations were 223.0, 12.1, 317.5 and 1053.5 μg/l at discharge, and decreased with BHT of 15.1, 20.8, 14.7, and 16.0 d, respectively. The results indicate that arsine was quickly metabolized to AsIII and subsequently up to DMA, with the result that the toxic effects of inorganic arsenic were added to those of arsine toxicity.

  8. Investigation of actinides speciation within the presence of ligands of interest for decorporation; Etude de la speciation des actinides vis-a-vis de ligands d'interet pour la decorporation

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L

    2008-01-15

    Data about the behaviour of actinides in biological media are required in order to investigate their decorporation. Those data are obtained through in vivo experiments and the study of chemical speciation of actinides within the presence of biological constituents. A part of this work consists in the development of a method leading to the determination of the speciation of actinides at the oxidation state +IV within the presence of a complexing species, as well as its structure. The method was applied to two types of ligands: 1) a constituent of blood plasma: the citrate anion. The various complexes formed were investigated and their formation constants were quantified. The coordination mode of the ligand was then clarified through a structural study of the complexes, underlining the role of only one carboxylic site and of the alcohol function. 2) chelating agents used for decorporation. The formation constants of complexes of An(IV) with NTA and DTPA were determined. The coordination number of the metallic cation in those complexes as well as the role of the nitrogen atom were proved. Lastly, the behaviour of Pu(IV) within the presence of LIHOPO was investigated. This chelating agent, more efficient than DTPA in the case of in vivo decorporation of Np, forms very stable complexes with the metallic cation. One of those complexes can be assumed to present a stoichiometry 2:3. (author)

  9. Predicting Metal Speciation & Bioavailability via Estimation of Metal-Organic Thermodynamic Properties

    Science.gov (United States)

    Prasad, A.; Howells, A. E.; Shock, E.

    2017-12-01

    The biological fate of any metal depends on its chemical form in the environment. Arsenic for example, is extremely toxic in the form of inorganic As+3 but completely benign in the organic form of arsenobetaine. Thus, given an exhaustive set of reactions and their equilibrium constants (logK), the bioavailability of any metal can be obtained for blood plasma, hydrothermal fluids or any system of interest. While many data exist for metal-inorganic ligands, logK data covering the temperature range of life for metal-organic complexes are sparse. Hence, we decided to estimate metal-organic logK values from correlations with the commonly available values of ligand pKa. Metal ion specific correlations were made with ligands classified according to their electron donor atoms, denticity and other chemical factors. While this approach has been employed before (Carbonaro et al. 2007, GCA 71, 3958-3968), new correlations were developed that provide estimates even when no metal-organic logK is available. In addition, we have used the same methods to make estimates of metal-organic entropy of association (ΔaS), which can provide logK for any temperature of biological relevance. Our current correlations employ logK and ΔaS data from 30 metal ions (like the biologically relevant Fe+3 & Zn+2) and 74 ligands (like formate and ethylenediamine), which can be expanded to estimate the metal-ligand reaction properties for these 30 metal ions with a possibly limitless number of ligands that may belong to our categories of ligands. With the help of such data, copper speciation was obtained for a defined growth medium for methanotrophs employed by Morton et al. (2000, AEM 66, 1730-1733) that agrees with experimental measurements showing that the free metal ion may not be the bioavailable form in all conditions. These results encourage us to keep filling the gaps in metal-organic logK data and continue finding relationships between biological responses (like metal-accumulation ratios

  10. Simultaneous tracing of 76Se-selenite and 77Se-selenomethionine by absolute labeling and speciation

    International Nuclear Information System (INIS)

    Suzuki, Kazuo T.; Somekawa, Layla; Kurasaki, Kazuki; Suzuki, Noriyuki

    2006-01-01

    Nutritional selenocompounds are transformed into the assumed common intermediate selenide, which is utilized for the synthesis of selenoenzymes or transformed into methylated metabolites for excretion. Hence, selenocompound metabolites can be traced only with labeled selenium. Here we applied a new tracer method for the metallomics of biometals using simultaneous speciation of each metallome labeled with different homo-elemental isotopes to metabolism and availability of selenium. Rats were depleted of endogenous natural abundance selenium by feeding a single selenium stable isotope ( 82 Se-selenite) and then administered 76 Se-selenite and 77 Se-selenomethionine ( 77 Se-SeMet)simultaneously. Biological samples were subjected to quantification and speciation analysis by HPLC-ICPMS. Metabolites of the labeled 76 Se and 77 Se and interaction with endogenous selenium were traced and examined without interference from the corresponding endogenous natural abundance isotopes. Differences in the distribution and metabolism among organs and between the two nutritional selenocompounds were compared under exactly identical biological and analytical conditions: (1) selenite was distributed more efficiently than SeMet in organs and body fluids except the pancreas. (2) SeMet was taken up by organs in its intact form. (3) Selenium of SeMet origin was distributed selectively in the pancreas and mostly bound to a protein together with intact SeMet. (4) Selenosugars A and B but not trimethylselenonium (TMSe) were detected in the liver. (5) Selenosugar B and TMSe were detected in the kidneys

  11. U(IV) fluorescence spectroscopy. A new speciation tool

    Energy Technology Data Exchange (ETDEWEB)

    Lehmann, Susanne; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Steudtner, Robin [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology

    2017-06-01

    We combined absorption and fluorescence spectroscopy to study the speciation of U(IV) in solution in concentrations down to 10{sup -6} M uranium. With our time-resolved laser-induced fluorescence setup we could determine the fluorescence decay time of U(IV) in perchloric as well as in chloric acid with 2.6 ± 0.3 ns at room temperature and 148.4 ± 6.5 ns at liquid nitrogen temperature. For the U(IV) sulfate system, we observed a bathochromic shift and a peak shape modification in the fluorescence spectra with increasing sulfate concentration in solution. Thus, the potential of U(IV) fluorescence for speciation analysis could be proven.

  12. Synergy between Allopatry and Ecology in Population Differentiation and Speciation

    Directory of Open Access Journals (Sweden)

    Yann Surget-Groba

    2012-01-01

    Full Text Available The general diversity pattern of the Caribbean anole radiation has been described in detail; however, the actual mechanisms at the origin of their diversification remain controversial. In particular, the role of ecological speciation, and the relative importance of divergence in allopatry and in parapatry, is debated. We describe the genetic structure of anole populations across lineage contact zones and ecotones to investigate the effect of allopatric divergence, natural selection, and the combination of both factors on population differentiation. Allopatric divergence had no significant impact on differentiation across the lineage boundary, while a clear bimodality in genetic and morphological characters was observed across an ecotone within a single lineage. Critically, the strongest differentiation was observed when allopatry and ecology act together, leading to a sharp reduction in gene flow between two lineages inhabiting different habitats. We suggest that, for Caribbean anoles to reach full speciation, a synergistic combination of several historical and ecological factors may be requisite.

  13. Determining uranium speciation in Fernald soils by molecular spectroscopic methods

    International Nuclear Information System (INIS)

    Allen, P.G.; Berg, J.M.; Crisholm-Brause, C.J.; Conradson, S.D.; Donohoe, R.J.; Morris, D.E.; Musgrave, J.A.; Tait, C.D.

    1994-07-01

    This progress report describes new experimental results and interpretations for data collected from October 1, 1992, through September 30, 1993, as part of the Characterization Task of the Uranium in Soils Integrated Demonstration of the Office of Technology Development, Office of Environmental Restoration and Waste Management of the US Department of Energy. X-ray absorption, optical luminescence, and Raman vibrational spectroscopies were used to determine uranium speciation in contaminated soils from the US DOE's former uranium production facility at Fernald, Ohio. These analyses were carried out both before and after application of one of the various decontamination technologies being developed within the Integrated Demonstration. This year the program focused on characterization of the uranium speciation remaining in the soils after decontamination treatment. X-ray absorption and optical luminescence spectroscopic data were collected for approximately 40 Fernald soil samples, which were treated by one or more of the decontamination technologies

  14. Speciation of Fe in ambient aerosol and cloudwater

    Energy Technology Data Exchange (ETDEWEB)

    Siefert, Ronald Lyn [California Inst. of Technology (CalTech), Pasadena, CA (United States)

    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.

  15. Microcolumn-based speciation analysis of thallium in soil and green cabbage.

    Science.gov (United States)

    Jia, Yanlong; Xiao, Tangfu; Sun, Jialong; Yang, Fei; Baveye, Philippe C

    2018-07-15

    Thallium (Tl) is a toxic trace metal, whose geochemical behavior and biological effects are closely controlled by its chemical speciation in the environment. However, little tends to be known about this speciation of Tl in soil and plant systems that directly affect the safety of food supplies. In this context, the objective of the present study was to elaborate an efficient method to separate and detect Tl(I) and Tl(III) species for soil and plant samples. This method involves the selective adsorption of Tl(I) on microcolumns filled with immobilized oxine, in the presence of DTPA (diethylenetriaminepentaacetic acid), followed by DTPA-enhanced ultrasonic and heating-induced extraction, coupled with ICP-MS detection. The method was characterized by a LOD of 0.037 μg/L for Tl(I) and 0.18 μg/L for Tl(III) in 10  mL samples. With this method, a second objective of the research was to assess the speciation of Tl in pot and field soils and in green cabbage crops. Experimental results suggest that DTPA extracted Tl was mainly present as Tl(I) in soils (>95%). Tl in hyperaccumulator plant green cabbage was also mainly present as Tl(I) (>90%). With respect to Tl uptake in plants, this study provides direct evidence that green cabbage mainly takes up Tl(I) from soil, and transports it into the aboveground organs. In soils, Tl(III) is reduced to Tl(I) even at the surface where the chemical environment promotes oxidation. This observation is conducive to understanding the mechanisms of Tl isotope fractionation in the soil-plant system. Based on geochemical fraction studies, the reducible fraction was the main source of Tl getting accumulated by plants. These results indicate that the improved analytical method presented in this study offers an economical, simple, fast, and sensitive approach for the separation of Tl species present in soils at trace levels. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Pu speciation in actual and simulated aged wastes

    Energy Technology Data Exchange (ETDEWEB)

    Lezama-pacheco, Juan S [Los Alamos National Laboratory; Conradson, Steven D [Los Alamos National Laboratory

    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.

  17. Speciation and gene flow between snails of opposite chirality.

    Directory of Open Access Journals (Sweden)

    Angus Davison

    2005-09-01

    Full Text Available Left-right asymmetry in snails is intriguing because individuals of opposite chirality are either unable to mate or can only mate with difficulty, so could be reproductively isolated from each other. We have therefore investigated chiral evolution in the Japanese land snail genus Euhadra to understand whether changes in chirality have promoted speciation. In particular, we aimed to understand the effect of the maternal inheritance of chirality on reproductive isolation and gene flow. We found that the mitochondrial DNA phylogeny of Euhadra is consistent with a single, relatively ancient evolution of sinistral species and suggests either recent "single-gene speciation" or gene flow between chiral morphs that are unable to mate. To clarify the conditions under which new chiral morphs might evolve and whether single-gene speciation can occur, we developed a mathematical model that is relevant to any maternal-effect gene. The model shows that reproductive character displacement can promote the evolution of new chiral morphs, tending to counteract the positive frequency-dependent selection that would otherwise drive the more common chiral morph to fixation. This therefore suggests a general mechanism as to how chiral variation arises in snails. In populations that contain both chiral morphs, two different situations are then possible. In the first, gene flow is substantial between morphs even without interchiral mating, because of the maternal inheritance of chirality. In the second, reproductive isolation is possible but unstable, and will also lead to gene flow if intrachiral matings occasionally produce offspring with the opposite chirality. Together, the results imply that speciation by chiral reversal is only meaningful in the context of a complex biogeographical process, and so must usually involve other factors. In order to understand the roles of reproductive character displacement and gene flow in the chiral evolution of Euhadra, it will be

  18. SOME SPECIATION STUDIES IN FOODSTUFF BY ATOMIC ABSORPTION SPECTROMETRY

    OpenAIRE

    Gücer, S

    2000-01-01

    There has been increasing interest in speciation studies of essentialelements in foods. The main limitation of this studies, their levels in foodsamples and the difficulties for the determination in their own differentforms without any changes in their original forms.Atomic Absorption Spectrometry (AAS) coupled with separation methodswould be outline in this presentation. Analytical scheme was given for tea, olive and garlic samples forManganese, Magnesium and Selenium respectively. Activated...

  19. Speciation of cadmium mixed ligand complexes in salt water lakes ...

    African Journals Online (AJOL)

    The experimentally determined shifts in half-wave potentials are used to compute several formation constants. At the natural [CO32-] of 0.5 M in the lake, the main contributor to the speciation of cadmium is [Cd(CO3Cl2)]2-. At high [Cd2+], the DPASV detects the presence of free Cd2+ ions, hence, potential polluting effect, ...

  20. Speciation, in the nuclear fuel cycle by spectroscopic techniques

    International Nuclear Information System (INIS)

    Colette, S.; Plancque, G.; Allain, F.; Lamouroux, C.; Steiner, V.; Amekraz, B.; Moulin, C.

    2000-01-01

    New analytical techniques allowing to perform speciation in the framework of the nuclear fuel cycle are more and more needed. They have to be selective (since matrix encountered are very complex), sensitive (in order to work at representative concentration and below solubility limit), as well as non intrusive (in order to keep the image of the real solution). Among them, laser-based analytical techniques present these advantages together with the possibility to perform remote measurements via fiber optics. Hence, Time-Resolved Laser-Induced Fluorescence (TRLIF) has been used for actinides/lanthanides interaction and speciation studies in inorganic and organic matrices from the reprocessing to waste storage. Moreover, new ion detection methods such as Electro-Spray - Mass Spectrometry (ES-MS) seems promising for speciation studies. Hence, it is the first time that it is possible to directly couple a liquid at atmospheric pressure to a mass detection working at reduced pressure with a soft mode of ionisation that should allow to give informations on chemical species present. Principle, advantages and limitations as well as results obtained with the use of TRLIF and ES-MS on different systems of interest including actinides, lanthanides, fission products in interaction with simple organic molecules to very complex structure will be presented and discussed. (authors)

  1. Speciation, in the nuclear fuel cycle by spectroscopic techniques

    Energy Technology Data Exchange (ETDEWEB)

    Colette, S.; Plancque, G.; Allain, F.; Lamouroux, C.; Steiner, V.; Amekraz, B.; Moulin, C. [CEA/Saclay, Dept, des Procedes d' Enrichissement (DPE), 91 - Gif-sur-Yvette (France)

    2000-07-01

    New analytical techniques allowing to perform speciation in the framework of the nuclear fuel cycle are more and more needed. They have to be selective (since matrix encountered are very complex), sensitive (in order to work at representative concentration and below solubility limit), as well as non intrusive (in order to keep the image of the real solution). Among them, laser-based analytical techniques present these advantages together with the possibility to perform remote measurements via fiber optics. Hence, Time-Resolved Laser-Induced Fluorescence (TRLIF) has been used for actinides/lanthanides interaction and speciation studies in inorganic and organic matrices from the reprocessing to waste storage. Moreover, new ion detection methods such as Electro-Spray - Mass Spectrometry (ES-MS) seems promising for speciation studies. Hence, it is the first time that it is possible to directly couple a liquid at atmospheric pressure to a mass detection working at reduced pressure with a soft mode of ionisation that should allow to give informations on chemical species present. Principle, advantages and limitations as well as results obtained with the use of TRLIF and ES-MS on different systems of interest including actinides, lanthanides, fission products in interaction with simple organic molecules to very complex structure will be presented and discussed. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

    Tipping, E. [Centre for Ecology and Hydrology, Lancaster Environment Centre, Library Avenue, Bailrigg, Lancaster LA1 4AP (United Kingdom)], E-mail: et@ceh.ac.uk; Vincent, C.D.; Lawlor, A.J.; Lofts, S. [Centre for Ecology and Hydrology, Lancaster Environment Centre, Library Avenue, Bailrigg, Lancaster LA1 4AP (United Kingdom)

    2008-12-15

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

  3. The role of male contest competition over mates in speciation

    Directory of Open Access Journals (Sweden)

    Anna QVARNSTRÖM, Niclas VALLIN, Andreas RUDH

    2012-06-01

    Full Text Available Research on the role of sexual selection in the speciation process largely focuses on the diversifying role of mate choice. In particular, much attention has been drawn to the fact that population divergence in mate choice and in the male traits subject to choice directly can lead to assortative mating. However, male contest competition over mates also constitutes an important mechanism of sexual selection. We review recent empirical studies and argue that sexual selection through male contest competition can affect speciation in ways other than mate choice. For example, biases in aggression towards similar competitors can lead to disruptive and negative frequency-dependent selection on the traits used in contest competition in a similar way as competition for other types of limited resources. Moreover, male contest abilities often trade-off against other abilities such as parasite resistance, protection against predators and general stress tolerance. Populations experiencing different ecological conditions should therefore quickly diverge non-randomly in a number of traits including male contest abilities. In resource based breeding systems, a feedback loop between competitive ability and habitat use may lead to further population divergence. We discuss how population divergence in traits used in male contest competition can lead to the build up of reproductive isolation through a number of different pathways. Our main conclusion is that the role of male contest competition in speciation remains largely scientifically unexplored [Current Zoology 58 (3: 490–506, 2012].

  4. Micronutrient metal speciation is driven by competitive organic chelation in grassland soils.

    Science.gov (United States)

    Boiteau, R.; Shaw, J. B.; Paša-Tolić, L.; Koppenaal, D.; Jansson, J.

    2017-12-01

    Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population.

  5. Dimethylthioarsinic anhydride: A standard for arsenic speciation

    International Nuclear Information System (INIS)

    Fricke, Michael; Zeller, Matthias; Cullen, William; Witkowski, Mark; Creed, John

    2007-01-01

    Dimethylthioarsinic acid (DMTA V ) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because of the unavailability of a well characterized standard. The synthesis of DMTA V was accomplished by the reaction of dimethylarsinic acid (DMA V ) with hydrogen sulfide. The initial reaction product produced is DMTA V but multiple products over the course of the reaction are also observed. Therefore, a chromatographic separation was developed to monitor the reaction progress via LC-ICP-MS. In this synthesis, conversion of DMA V to DMTA V was not taken to completion to avoid the production of side products. The product was isolated from the starting material by standard organic techniques. Single crystal diffraction demonstrated that solid DMTA V is present in the form of the oxygen-bridged dimethylthioarsinic anhydride. Dissolution of the anhydride in water produces the acid form of DMTA V and the aqueous phase DMTA V provided a characteristic molecular ion of m/z 155 by LC-ESI-MS. The synthesis and isolation of dimethylthioarsinic anhydride provides a stable crystalline standard suitable for identification, toxicological study and exposure assessment of dimethylthioarsinic acid

  6. Dimethylthioarsinic anhydride: A standard for arsenic speciation

    Energy Technology Data Exchange (ETDEWEB)

    Fricke, Michael [United States Environmental Protection Agency, National Exposure Research Laboratory, Microbiological and Chemical Exposure Assessment Research Division, 26 W. Martin Luther King Drive, Cincinnati, OH 45268 (United States); Zeller, Matthias [STaRBURSTT-Cyberdiffraction Consortium, Department of Chemistry, Youngstown State University, One University Plaza, Youngstown, OH 44555-3663 (United States); Cullen, William [Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1 (Canada); Witkowski, Mark [Food and Drug Administration, Forensic Chemistry Center, Vibrational Spectroscopy Laboratory, 6751 Steger Drive, Cincinnati, OH 45237 (United States); Creed, John [United States Environmental Protection Agency, National Exposure Research Laboratory, Microbiological and Chemical Exposure Assessment Research Division, 26 W. Martin Luther King Drive, Cincinnati, OH 45268 (United States)]. E-mail: creed.jack@epa.gov

    2007-01-30

    Dimethylthioarsinic acid (DMTA{sup V}) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because of the unavailability of a well characterized standard. The synthesis of DMTA{sup V} was accomplished by the reaction of dimethylarsinic acid (DMA{sup V}) with hydrogen sulfide. The initial reaction product produced is DMTA{sup V} but multiple products over the course of the reaction are also observed. Therefore, a chromatographic separation was developed to monitor the reaction progress via LC-ICP-MS. In this synthesis, conversion of DMA{sup V} to DMTA{sup V} was not taken to completion to avoid the production of side products. The product was isolated from the starting material by standard organic techniques. Single crystal diffraction demonstrated that solid DMTA{sup V} is present in the form of the oxygen-bridged dimethylthioarsinic anhydride. Dissolution of the anhydride in water produces the acid form of DMTA{sup V} and the aqueous phase DMTA{sup V} provided a characteristic molecular ion of m/z 155 by LC-ESI-MS. The synthesis and isolation of dimethylthioarsinic anhydride provides a stable crystalline standard suitable for identification, toxicological study and exposure assessment of dimethylthioarsinic acid.

  7. Plutonium speciation affected by environmental bacteria

    International Nuclear Information System (INIS)

    Neu, M.P.; Icopini, G.A.; Boukhalfa, H.

    2005-01-01

    Plutonium has no known biological utility, yet it has the potential to interact with bacterial cellular and extracellular structures that contain metal-binding groups, to interfere with the uptake and utilization of essential elements, and to alter cell metabolism. These interactions can transform plutonium from its most common forms, solid, mineral-adsorbed, or colloidal Pu(IV), to a variety of biogeochemical species that have much different physico-chemical properties. Organic acids that are extruded products of cell metabolism can solubilize plutonium and then enhance its environmental mobility, or in some cases facilitate plutonium transfer into cells. Phosphate- and carboxylate-rich polymers associated with cell walls can bind plutonium to form mobile biocolloids or Pu-laden biofilm/mineral solids. Bacterial membranes, proteins or redox agents can produce strongly reducing electrochemical zones and generate molecular Pu(III/IV) species or oxide particles. Alternatively, they can oxidize plutonium to form soluble Pu(V) or Pu(VI) complexes. This paper reviews research on plutonium-bacteria interactions and closely related studies on the biotransformation of uranium and other metals. (orig.)

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

    Science.gov (United States)

    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

  9. Neptunium speciation (complexation and redox behaviour) in aqueous citrate medium

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L.; Ansoborlo, E.; Moisy, Ph. [CEA Marcoule (France)

    2005-07-01

    Full text of publication follows: In the framework of the French Environmental Nuclear Toxicology programme, additional experiments related to the decorporation of actinides are planned. The lack of information on the neptunium behaviour within blood and the inefficiency of therapeutic treatments, led us to study the complexation of this element with basic anions. Within this purpose, the in vitro behaviour of Np{sup IV} and Np{sup V} in simple media simulating biological media was studied: blood plasma is one of the media of interest and it can be simulated, from a chemical point of view, by an aqueous solution with pH 7.4, containing ions such as citrate (1.6 10{sup -4} mol/L), lactate (1.5 10{sup -3} mol/L), CO{sub 3}{sup 2-} (2.5 10{sup -2} mol/L), PO{sub 4}{sup 3-} (1.1 10{sup -3} mol/L), SO{sub 4}{sup 2-} (3.3 10{sup -4} mol/L) and Cl{sup -} (9 10{sup -2} mol/L). This study was more specifically focused on the behaviour of neptunium with citrate ion, which is also a basic ligand to consider when one wishes to study the migration of actinides in the environment, since it exists in significant amounts in the ground due to its production by the plants. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np{sup V} with various acid-basic forms of the citrate anion was observed; regarding Np{sup IV}, two complexes, with 1:1 and 1:2 stoichiometry, have been respectively observed. The reactivity of Np{sup VI} is probably similar to the behaviour of U{sup VI}, which is reported in literature to form a complex with a 1:1 stoichiometry with the Cit{sup 3-}anion From the quantitative study of these equilibria, it has been possible to determine the values of various equilibrium constants. Concerning the stability of neptunium towards oxido-reduction, it was confirmed that Np{sup VI} was very quickly reduced to Np{sup V} by the citrate anions

  10. Geologic drivers of late ordovician faunal change in laurentia: investigating links between tectonics, speciation, and biotic invasions.

    Directory of Open Access Journals (Sweden)

    David F Wright

    Full Text Available Geologic process, including tectonics and global climate change, profoundly impact the evolution of life because they have the propensity to facilitate episodes of biogeographic differentiation and influence patterns of speciation. We investigate causal links between a dramatic faunal turnover and two dominant geologic processes operating within Laurentia during the Late Ordovician: the Taconian Orogeny and GICE related global cooling. We utilize a novel approach for elucidating the relationship between biotic and geologic changes using a time-stratigraphic, species-level evolutionary framework for articulated brachiopods from North America. Phylogenetic biogeographic analyses indicate a fundamental shift in speciation mode-from a vicariance to dispersal dominated macroevolutionary regime-across the boundary between the Sandbian to Katian Stages. This boundary also corresponds to the onset of renewed intensification of tectonic activity and mountain building, the development of an upwelling zone that introduced cool, nutrient-rich waters into the epieric seas of eastern Laurentia, and the GICE isotopic excursion. The synchronicity of these dramatic geologic, oceanographic, and macroevolutionary changes supports the influence of geologic events on biological evolution. Together, the renewed tectonic activity and oceanographic changes facilitated fundamental changes in habitat structure in eastern North America that reduced opportunities for isolation and vicariance. They also facilitated regional biotic dispersal of taxa that led to the subsequent establishment of extrabasinal (=invasive species and may have led to a suppression of speciation within Laurentian faunas. Phylogenetic biogeographic analysis further indicates that the Richmondian Invasion was a multidirectional regional invasion event that involved taxa immigrating into the Cincinnati region from basins located near the continental margins and within the continental interior.

  11. Applicability of multisyringe chromatography coupled to cold-vapor atomic fluorescence spectrometry for mercury speciation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Guzman-Mar, J.L.; Hinojosa-Reyes, L. [Department of Chemistry Sciences, Universidad Autonoma de Nuevo Leon, Cd. Universitaria, Pedro de Alba s/n, C.P. 66451 San Nicolas de los Garza, Nuevo Leon (Mexico); Serra, A.M. [Department of Chemistry, University of the Balearic Islands, E-07122 Palma de Mallorca (Spain); Hernandez-Ramirez, A. [Department of Chemistry Sciences, Universidad Autonoma de Nuevo Leon, Cd. Universitaria, Pedro de Alba s/n, C.P. 66451 San Nicolas de los Garza, Nuevo Leon (Mexico); Cerda, V., E-mail: victor.cerda@uib.es [Department of Chemistry, University of the Balearic Islands, E-07122 Palma de Mallorca (Spain)

    2011-12-05

    Graphical abstract: An automatic system, based on the applicability of multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) detection is developed for mercury speciation. Highlights: Black-Right-Pointing-Pointer The on-line coupling of MSC to CV/AFS was developed for mercury speciation analysis. Black-Right-Pointing-Pointer The speciation of MeHg{sup +}, Hg{sup 2+} and EtHg{sup +} was achieved on a RP C18 monolithic column. Black-Right-Pointing-Pointer The hyphenated system provided higher sample throughput compared to HPLC-CV/AFS. Black-Right-Pointing-Pointer The limits of detection for mercury species were comparable or better than those reported by HPLC-CV/AFS. Black-Right-Pointing-Pointer The developed method also provided low instrumental and operational costs. - Abstract: In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg{sup 2+}), methylmercury (MeHg{sup +}) and ethylmercury (EtHg{sup +}) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3{sigma}) were found to be 0.03, 0.11 and 0.09 {mu}g L{sup -1} for MeHg{sup +}, Hg{sup 2+} and EtHg{sup +}, respectively. The relative standard deviation (RSD, n = 6) of the

  12. The effects of metamorphism on iron mineralogy and the iron speciation redox proxy

    Science.gov (United States)

    Slotznick, Sarah P.; Eiler, John M.; Fischer, Woodward W.

    2018-03-01

    As the most abundant transition metal in the Earth's crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite's identification depended on the extraction techniques

  13. Nickel speciation in cement-stabilized/solidified metal treatment filtercakes

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Amitava, E-mail: reroy@lsu.edu [J. Bennett Johnston, Sr., Center for Advanced Microstructures and Devices, Louisiana State University, Baton Rouge, LA 70806, USA (United States); Stegemann, Julia A., E-mail: j.stegemann@ucl.ac.uk [Centre for Resource Efficiency & the Environment, Department of Civil, Environmental & Geomatic Engineering, University College London, Chadwick Building, Gower Street, London WC1E 6BT, UK (United Kingdom)

    2017-01-05

    Highlights: • XAS shows the same Ni speciation in untreated and stabilized/solidified filtercake. • Ni solubility is the same for untreated and stabilized/solidified filtercake. • Leaching is controlled by pH and physical encapsulation for all binders. - Abstract: Cement-based stabilization/solidification (S/S) is used to decrease environmental leaching of contaminants from industrial wastes. In this study, two industrial metal treatment filtercakes were characterized by X-ray diffractometry (XRD), thermogravimetric and differential thermogravimetric analysis (TG/DTG) and Fourier transform infrared (FTIR); speciation of nickel was examined by X-ray absorption (XAS) spectroscopy. Although the degree of carbonation and crystallinity of the two untreated filtercakes differed, α-nickel hydroxide was identified as the primary nickel-containing phase by XRD and nickel K edge XAS. XAS showed that the speciation of nickel in the filtercake was unaltered by treatment with any of five different S/S binder systems. Nickel leaching from the untreated filtercakes and all their stabilized/solidified products, as a function of pH in the acid neutralization capacity test, was essentially complete below pH ∼5, but was 3–4 orders of magnitude lower at pH 8–12. S/S does not respeciate nickel from metal treatment filtercakes and any reduction of nickel leaching by S/S is attributable to pH control and physical mechanisms only. pH-dependent leaching of Cr, Cu and Ni is similar for the wastes and s/s products, except that availability of Cr, Cu and Zn at decreased pH is reduced in matrices containing ground granulated blast furnace slag.

  14. Phylogenetic niche conservatism and the evolutionary basis of ecological speciation.

    Science.gov (United States)

    Pyron, R Alexander; Costa, Gabriel C; Patten, Michael A; Burbrink, Frank T

    2015-11-01

    Phylogenetic niche conservatism (PNC) typically refers to the tendency of closely related species to be more similar to each other in terms of niche than they are to more distant relatives. This has been implicated as a potential driving force in speciation and other species-richness patterns, such as latitudinal gradients. However, PNC has not been very well defined in most previous studies. Is it a pattern or a process? What are the underlying endogenous (e.g. genetic) and exogenous (e.g. ecological) factors that cause niches to be conserved? What degree of similarity is necessary to qualify as PNC? Is it possible for the evolutionary processes causing niches to be conserved to also result in niche divergence in different habitats? Here, we revisit these questions, codifying a theoretical and operational definition of PNC as a mechanistic evolutionary process resulting from several factors. We frame this both from a macroevolutionary and population-genetic perspective. We discuss how different axes of physical (e.g. geographic) and environmental (e.g. climatic) heterogeneity interact with the fundamental process of PNC to produce different outcomes of ecological speciation. We also review tests for PNC, and suggest ways that these could be improved or better utilized in future studies. Ultimately, PNC as a process has a well-defined mechanistic basis in organisms, and future studies investigating ecological speciation would be well served to consider this, and frame hypothesis testing in terms of the processes and expected patterns described herein. The process of PNC may lead to patterns where niches are conserved (more similar than expected), constrained (divergent within a limited subset of available niches), or divergent (less similar than expected), based on degree of phylogenetic relatedness between species. © 2014 Cambridge Philosophical Society.

  15. Miscibility and Speciation in the Water/carbon Dioxide System

    Science.gov (United States)

    Abramson, E.; Bollengier, O.; Brown, J. M.

    2017-12-01

    We have been exploring fluid-fluid solubilities and speciation in mixed systems of CO2-H2O. Fluid-fluid immiscibility extends to the highest pressures and temperatures yet explored (7 GPa, 700K). In this region, commonly used COH fluid models agree neither with the data nor among themselves. The range of immiscibility is extended by addition of NaCl, but miscibility limits determined in preliminary experiments are not as expected from extrapolation of lower pressure (linked to an observed change in speciation as CO2(aq) reacts with water. The identity of the newly formed species is, as of the writing of this abstract, unknown, but presumed to be either H2CO3 or HCO3-. A reasonable match between the observed equilibria and an application of HKF theory suggests that the new species is, indeed, HCO3-, but with a Raman frequency shifted from that found in the dilute aqueous solution. Application of HKF theory to the CO2(f)-CO2(aq) equilibrium suffers from an incompatibility of the usual formulation of the theory with known molar volumes of CO2(f) at higher pressures. On the basis of these studies we conclude that models of CO2-H2O fluids must take into account major changes in speciation, and that simple equations-of-state, of a few fitted parameters, will not afford an adequate description of such fluids. "First principles" models, tested against real data, seem more likely to yield the desired results. This statement extends as well to the calculation of the dielectric constants of these mixed fluids, the basis of ionic solution chemistry. Further, semi-empirical formulations of solution thermodynamics, which function well at pressures of kbars, ought to be re-worked for use over larger pressure ranges.

  16. Genetic evidence for hybrid trait speciation in heliconius butterflies.

    Directory of Open Access Journals (Sweden)

    Camilo Salazar

    2010-04-01

    Full Text Available Homoploid hybrid speciation is the formation of a new hybrid species without change in chromosome number. So far, there has been a lack of direct molecular evidence for hybridization generating novel traits directly involved in animal speciation. Heliconius butterflies exhibit bright aposematic color patterns that also act as cues in assortative mating. Heliconius heurippa has been proposed as a hybrid species, and its color pattern can be recreated by introgression of the H. m. melpomene red band into the genetic background of the yellow banded H. cydno cordula. This hybrid color pattern is also involved in mate choice and leads to reproductive isolation between H. heurippa and its close relatives. Here, we provide molecular evidence for adaptive introgression by sequencing genes across the Heliconius red band locus and comparing them to unlinked wing patterning genes in H. melpomene, H. cydno, and H. heurippa. 670 SNPs distributed among 29 unlinked coding genes (25,847bp showed H. heurippa was related to H. c. cordula or the three species were intermixed. In contrast, among 344 SNPs distributed among 13 genes in the red band region (18,629bp, most showed H. heurippa related with H. c. cordula, but a block of around 6,5kb located in the 3' of a putative kinesin gene grouped H. heurippa with H. m. melpomene, supporting the hybrid introgression hypothesis. Genealogical reconstruction showed that this introgression occurred after divergence of the parental species, perhaps around 0.43Mya. Expression of the kinesin gene is spatially restricted to the distal region of the forewing, suggesting a mechanism for pattern regulation. This gene therefore constitutes the first molecular evidence for adaptive introgression during hybrid speciation and is the first clear candidate for a Heliconius wing patterning locus.

  17. Modelling interaction of deep groundwaters with bentonite and radionuclide speciation

    International Nuclear Information System (INIS)

    Wanner, H.

    1986-04-01

    In the safety analysis recently reported for a potential Swiss high-level waste repository, radionuclide speciation and solubility limits are calculated for expected granitic groundwater conditions. With the objective of deriving a more realistic description of radionuclide release from the near-field, an investigation has been initiated to quantitatively specify the chemistry of the near-field. In the Swiss case, the main components of the near-field are the glass waste-matrix, a thick steel canister horizontally emplaced in a drift, and a backfill of highly compacted sodium bentonite. This report describes a thermodynamic model which is used to estimate the chemical composition of the pore water in compacted sodium bentonite. Solubility limits and speciation of important actinides and the fission product technetium in the bentonite pore water are then calculated. The model is based on available experimental data on the interaction of sodium bentonite and groundwater and represents means of extrapolation from laboratory data to repository conditions. The modelled composition of the pore water of compacted sodium bentonite, as well as the various compositions resulting from the long-term extrapolation, are used to estimate radionuclide solubilities in the near-field of a deep repository. From the chemical point of view, calcium bentonite seems to be more stable than sodium bentonite in the presence of Swiss Reference Groundwater. Since the effect of calcium bentonite on the groundwater chemical composition will be considerably less marked than that of sodium bentonite, especially with respect to key parameters for the nuclide speciation like carbonate concentration and pH, the use of calcium bentonite instead of sodium bentonite will improve the reliability in the prediction of source terms for radionuclide transport in the geosphere. (author)

  18. Biological Agents

    Science.gov (United States)

    ... E-Tools Safety and Health Topics / Biological Agents Biological Agents This page requires that javascript be enabled ... 202) 693-2300 if additional assistance is required. Biological Agents Menu Overview In Focus: Ebola Frederick A. ...

  19. Trace metal speciation: Finally, correctly addressing trace metal issues

    International Nuclear Information System (INIS)

    Donard, O.F.X.

    2001-01-01

    The history of the development of trace metal speciation was discussed and the reasons behind the relatively slow widespread acceptance of its importance were presented. Partially, this was due to the lack of availability of commercial instrumentation and partly to the drive towards improving sensitivity in analytical chemistry which had focused attention on total concentration determinations. The sophistication and control of analytical instrumentation is now such that the spotlight must be turned onto the chemical species of an element present in a sample since this is what governs its behaviour in the biosphere. Indeed, several companies are currently considering the introduction of instrumentation specifically designed for metal species determination

  20. WHATIF-AQ, Geochem Speciation and Saturation of Aqueous Solution

    International Nuclear Information System (INIS)

    Nielsen, Ole John; Jensen, Bror Skytte

    1988-01-01

    1 - Description of program or function: WHATIF-AQ is part of a family of programs for calculations of geochemistry in the near-field of radioactive waste with temperature gradients. The program calculates speciation and saturation indices for an aqueous solution at temperatures in the range 0 - 125 degrees C. The chemical equilibrium is determined by solving a set of nonlinear equations consisting of the equilibrium constant and mass balance constraints. 2 - Method of solution: The set of equations is solved using a generalized Newton-Raphson technique

  1. Chemical speciation and transformation of mercury in contaminated sediments

    OpenAIRE

    Drott, Andreas

    2009-01-01

    Biomagnification of mercury (Hg) in aquatic food webs occurs almost exclusively as mono-methyl Hg (MeHg). In this thesis, the influence of chemical speciation and environmental conditions on transformations of inorganic Hg (HgII) and MeHg was studied at eight sites in Sweden with Hg contaminated sediments. The source of contamination was either Hg0(l) or phenyl-Hg, and total Hg concentrations ranged between 1.0-1100 nmol g-1. The environmental conditions, e.g. salinity, temperature climate, p...

  2. Inferring speciation modes in a clade of Iberian chafers from rates of morphological evolution in different character systems

    Directory of Open Access Journals (Sweden)

    Ahrens Dirk

    2009-09-01

    Full Text Available Abstract Background Studies of speciation mode based on phylogenies usually test the predicted effect on diversification patterns or on geographical distribution of closely related species. Here we outline an approach to infer the prevalent speciation mode in Iberian Hymenoplia chafers through the comparison of the evolutionary rates of morphological character systems likely to be related to sexual or ecological selection. Assuming that mitochondrial evolution is neutral and not related to measured phenotypic differences among the species, we contrast hypothetic outcomes of three speciation modes: 1 geographic isolation with subsequent random morphological divergence, resulting in overall change proportional to the mtDNA rate; 2 sexual selection on size and shape of the male intromittent organs, resulting in an evolutionary rate decoupled to that of the mtDNA; and 3 ecological segregation, reflected in character systems presumably related to ecological or biological adaptations, with rates decoupled from that of the mtDNA. Results The evolutionary rate of qualitative external body characters was significantly correlated to that of the mtDNA both for the overall root-to-tip patristic distances and the individual inter-node branches, as measured with standard statistics and the randomization of a global comparison metric (the z-score. The rate of the body morphospace was significantly correlated to that of the mtDNA only for the individual branches, but not for the patristic distances, while that of the paramere outline was significantly correlated with mtDNA rates only for the patristic distances but not for the individual branches. Conclusion Structural morphological characters, often used for species recognition, have evolved at a rate proportional to that of the mtDNA, with no evidence of directional or stabilising selection according to our measures. The change in body morphospace seems to have evolved randomly at short term, but the overall

  3. Temporal variability in Cu speciation, phytotoxicity, and soil microbial activity of Cu-polluted soils as affected by elevated temperature.

    Science.gov (United States)

    Fu, Qing-Long; Weng, Nanyan; Fujii, Manabu; Zhou, Dong-Mei

    2018-03-01

    Global warming has obtained increasing attentions due to its multiple impacts on agro-ecosystem. However, limited efforts had been devoted to reveal the temporal variability of metal speciation and phytotoxicity of heavy metal-polluted soils affected by elevated temperature under the global warming scenario. In this study, effects of elevated temperature (15 °C, 25 °C, and 35 °C) on the physicochemical properties, microbial metabolic activities, and phytotoxicity of three Cu-polluted soils were investigated by a laboratory incubation study. Soil physicochemical properties were observed to be significantly altered by elevated temperature with the degree of temperature effect varying in soil types and incubation time. The Biolog and enzymatic tests demonstrated that soil microbial activities were mainly controlled and decreased with increasing incubation temperature. Moreover, plant assays confirmed that the phytotoxicity and Cu uptake by wheat roots were highly dependent on soil types but less affected by incubation temperature. Overall, the findings in this study have highlighted the importance of soil types to better understand the temperature-dependent alternation of soil properties, Cu speciation and bioavailability, as well as phytotoxicity of Cu-polluted soils under global warming scenario. The present study also suggests the necessary of investigating effects of soil types on the transport and accumulation of toxic elements in soil-crop systems under global warming scenario. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Evolution of blind beetles in isolated aquifers: a test of alternative modes of speciation

    NARCIS (Netherlands)

    Leys, R.; Nes, van E.H.; Watts, C.H.; Cooper, S.J.B.; Humphreys, W.F.; Hogendoorn, K.

    2012-01-01

    Evidence is growing that not only allopatric but also sympatric speciation can be important in the evolution of species. Sympatric speciation has most convincingly been demonstrated in laboratory experiments with bacteria, but field-based evidence is limited to a few cases. The recently discovered

  5. Comparison of analytical charge-form and equilibrium thermodynamic speciation of certain radionuclides

    International Nuclear Information System (INIS)

    Jenne, E.A.; Cowan, C.E.; Robertson, D.E.

    1984-01-01

    Calculating trace element speciation with a thermodynamic model is often challenged on the basis that the existing thermodynamic data are not sufficiently reliable. Water quality data and corresponding analytical charge-form speciation analysis were available for radionuclides occurring in a low-level radioactive groundwater. This offered an opportunity for comparing the results of an equilibrium thermodynamic model with the results of analytical charge-form speciation. The charge-form speciation was determined using the Battelle Large Volume Water Sampler, which contains consecutive layers of cation resin, anion resin and activated aluminum oxide for retention of cationic, anionic and non-ionic dissolved chemical species, respectively. The thermodynamic speciation of Cs, Cr, Fe, I, Mn, Mo, Na, and Zn was calculated using the MINTEQ geochemical model. Ce, Co, Tc, Np, Pm, and Sb were speciated by hand calculation. Excellent agreement between the analytically determined charge-form and the thermodynamic speciation was observed for 54 Mn, 144 Ce, 131 I, 24 Na, 137 Cs, 99 Mo, 99 Tc, 151 Pm, 239 Np. Organic complexation by natural and/or synthetic organics in the waters may be important in the speciation of 65 An, 60 Co, 131 I, 59 Fe and possibly 51 Cr. Both 124 Sb and 125 Sb appeared to be in redox disequilibria with the groundwater. 29 references, 2 tables

  6. Recent Developments in the Speciation and Determination of Mercury Using Various Analytical Techniques

    Directory of Open Access Journals (Sweden)

    Lakshmi Narayana Suvarapu

    2015-01-01

    Full Text Available This paper reviews the speciation and determination of mercury by various analytical techniques such as atomic absorption spectrometry, voltammetry, inductively coupled plasma techniques, spectrophotometry, spectrofluorometry, high performance liquid chromatography, and gas chromatography. Approximately 126 research papers on the speciation and determination of mercury by various analytical techniques published in international journals since 2013 are reviewed.

  7. Mimetic Divergence and the Speciation Continuum in the Mimic Poison Frog Ranitomeya imitator

    DEFF Research Database (Denmark)

    Twomey, Evan; Vestergaard, Jacob Schack; Venegas, Pablo J.

    2016-01-01

    While divergent ecological adaptation can drive speciation, understanding the factors that facilitate or constrain this process remains a major goal in speciation research. Here, we study two mimetic transition zones in the poison frog Ranitomeya imitator, a species that has undergone a Mullerian...

  8. Influence of EDDS on metal speciation in soil extracts: Measurement and mechanistic multicomponent modeling

    NARCIS (Netherlands)

    Koopmans, G.F.; Schenkeveld, W.D.C.; Song, J.; Luo, Y.; Japenga, J.; Temminghoff, E.J.M.

    2008-01-01

    The use of the [S,S]-isomer of EDDS to enhance phytoextraction has been proposed for the remediation of heavy metal contaminated soils. Speciation of metals in soil solution in the presence of EDDS and dissolved organic matter (DOM) received, however, almost no attention, whereas metal speciation

  9. Chemical speciation of L-glutamine complexes with Co(II), Ni(II) and ...

    African Journals Online (AJOL)

    The trend in the variation of stability constants of the complexes with mole fraction of the surfactant is attributed to the compartmentalization of complexation equilibria. Distribution of species and effect of influential parameters on chemical speciation have also been presented. KEY WORDS: Chemical speciation, complex ...

  10. EPA’s SPECIATE 4.4 Database - Development and Uses

    Science.gov (United States)

    SPECIATE is the EPA's repository of TOG, PM, and Other Gases speciation profiles of air pollution sources. It includes weight fractions of both organic species and PM and provides data in consistent units. Species include metals, ions, elements, and organic and inorganic compound...

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

    OpenAIRE

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

    2015-01-01

    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 contri...

  12. HPLC inorganic arsenic speciation analysis of samples containing high sulfuric acid and iron levels

    NARCIS (Netherlands)

    Gonzalez-Contreras, P.A.; Gerrits, I.P.A.M.; Weijma, J.; Buisman, C.J.N.

    2011-01-01

    To monitor the oxidation of arsenite to arsenate in oxidizing and bioleaching reactors, speciation analysis of the inorganic arsenic compounds is required. Existing arsenic speciation analysis techniques are based on the use of liquid chromatography columns coupled to detector equipment such as

  13. Speciation analysis of 129I in seawater using coprecipitation and accelerator mass spectrometry and its applications

    DEFF Research Database (Denmark)

    Xing, Shan; Hou, Xiaolin; Aldahan, Ala

    2017-01-01

    Speciation analysis of long-lived 129I in seawater can provide useful information on the source of water masses. This paper presents an improved method for speciation analysis of 129I based on coprecipitation of iodide as AgI with Ag2SO3 and AgCl. By adding a small amount of 127I carrier...

  14. Speciation driven by hybridization and chromosomal plasticity in a wild yeast.

    Science.gov (United States)

    Leducq, Jean-Baptiste; Nielly-Thibault, Lou; Charron, Guillaume; Eberlein, Chris; Verta, Jukka-Pekka; Samani, Pedram; Sylvester, Kayla; Hittinger, Chris Todd; Bell, Graham; Landry, Christian R

    2016-01-11

    Hybridization is recognized as a powerful mechanism of speciation and a driving force in generating biodiversity. However, only few multicellular species, limited to a handful of plants and animals, have been shown to fulfil all the criteria of homoploid hybrid speciation. This lack of evidence could lead to the interpretation that speciation by hybridization has a limited role in eukaryotes, particularly in single-celled organisms. Laboratory experiments have revealed that fungi such as budding yeasts can rapidly develop reproductive isolation and novel phenotypes through hybridization, showing that in principle homoploid speciation could occur in nature. Here, we report a case of homoploid hybrid speciation in natural populations of the budding yeast Saccharomyces paradoxus inhabiting the North American forests. We show that the rapid evolution of chromosome architecture and an ecological context that led to secondary contact between nascent species drove the formation of an incipient hybrid species with a potentially unique ecological niche.

  15. Speciation environments and centres of diversity in southern Africa. I. Conceptual framework

    Directory of Open Access Journals (Sweden)

    E. R. Robinson

    1982-10-01

    Full Text Available A knowledge of the nature and distribution of the environments where speciation (micro-evolution is or has been rapid would help explain plant distributions and give insight into the mechanisms of plant evolution. Before southern African speciation environments can be identified and described, a number of basic theoretical concepts have to be clarified. In this paper the major taxonomic, systematic, floristic, ecological and evolutionary ideas pertinent to speciation environments are reviewed and discussed. Despite many publications about species concepts, species diversity, modes of speciation and the relationship between environments and genetic variability within taxa, it is still not possible to make predictions about the kinds of environments that favour speciation.

  16. Review: Speciation in the myrtle family (Myrtaceae: rapid and slow models

    Directory of Open Access Journals (Sweden)

    PUDJI WIDODO

    2007-01-01

    Full Text Available Speciation or formation of new species is a process which may take very long time. When a new species is really formed from a previous species is still unknown exactly. However, sometimes when populations no longer interbreed, they are thought to be separate species. As natural selection, if populations adapt the occupying different environments, they will diverge into races, subspecies, and finally separate species. There are some models of speciation such as geographical, polyploidy, chromosomal, and ecological speciation. However, in the myrtle family (Myrtaceae they can be grouped into two big models of speciation namely the rapid and slow speciation. This review points out that hybridization is a major factor affecting Myrtaceae, although evolution activities were also approved by the fact that some fossil pollens have been found in Antartica

  17. Review of speciation and solubility of radionuclides in the near and far field. Pt. 2

    International Nuclear Information System (INIS)

    Smith-Briggs, J.L.

    1992-01-01

    This report represents Part 2 in a series of three reports which review the speciation and solubility of radionuclides in the near and far field. Part 2 is a general bibliography from 1978 to 1991. This report contains the bibliography for the review of speciation and solubility radionuclides in the near and far field from 1978 to 1991. The importance of the solubility and speciation of radionuclides in relation to the safety assessment of the repository is discussed. Solubility is defined, both theoretically and pragmatically, and the factors which influence solubility and speciation are discussed. The literature search was performed using the INIS database. The UKAEA RECAP database, the NIREX report bibliography and a list of DOE reports provided by the DOE were also used. The bibliography is divided into five sections, solubility and speciation experimental data, basic thermodynamic data, solubility limiting solid phases, experimental design and review and overview articles. Some references appear in more than one section. (Author)

  18. Divergence with gene flow across a speciation continuum of Heliconius butterflies.

    Science.gov (United States)

    Supple, Megan A; Papa, Riccardo; Hines, Heather M; McMillan, W Owen; Counterman, Brian A

    2015-09-24

    A key to understanding the origins of species is determining the evolutionary processes that drive the patterns of genomic divergence during speciation. New genomic technologies enable the study of high-resolution genomic patterns of divergence across natural speciation continua, where taxa pairs with different levels of reproductive isolation can be used as proxies for different stages of speciation. Empirical studies of these speciation continua can provide valuable insights into how genomes diverge during speciation. We examine variation across a handful of genomic regions in parapatric and allopatric populations of Heliconius butterflies with varying levels of reproductive isolation. Genome sequences were mapped to 2.2-Mb of the H. erato genome, including 1-Mb across the red color pattern locus and multiple regions unlinked to color pattern variation. Phylogenetic analyses reveal a speciation continuum of pairs of hybridizing races and incipient species in the Heliconius erato clade. Comparisons of hybridizing pairs of divergently colored races and incipient species reveal that genomic divergence increases with ecological and reproductive isolation, not only across the locus responsible for adaptive variation in red wing coloration, but also at genomic regions unlinked to color pattern. We observe high levels of divergence between the incipient species H. erato and H. himera, suggesting that divergence may accumulate early in the speciation process. Comparisons of genomic divergence between the incipient species and allopatric races suggest that limited gene flow cannot account for the observed high levels of divergence between the incipient species. Our results provide a reconstruction of the speciation continuum across the H. erato clade and provide insights into the processes that drive genomic divergence during speciation, establishing the H. erato clade as a powerful framework for the study of speciation.

  19. Uranium speciation in biofilms studies by laser fluorescence techniques

    International Nuclear Information System (INIS)

    Arnold, Thuro; Grossmann, Kay; Baumann, Nils

    2010-01-01

    Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behaviour. The mechanisms of these processes are currently not understood, because the complexity of such biofilms creates many discrete geochemical microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical properties, e.g. pH and dissolved oxygen concentration, the presence of organic molecules, e.g. metabolites, and many more, all of which may affect metal speciation. To obtain such information, which is necessary for performance assessment studies or the development of new cost-effective strategies for cleaning waste waters, it is very important to develop new non-invasive methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques have some superior features, above all very high sensitivity for fluorescent heavy metals. An approach combining confocal laser scanning microscopy and laser-induced fluorescence spectroscopy for study of the interactions of biofilms with uranium is presented. It was found that coupling these techniques furnishes a promising tool for in-situ non-invasive study of fluorescent heavy metals within biofilm systems. Information on uranium speciation and uranium redox states can be obtained.

  20. Quantifying variation in speciation and extinction rates with clade data.

    Science.gov (United States)

    Paradis, Emmanuel; Tedesco, Pablo A; Hugueny, Bernard

    2013-12-01

    High-level phylogenies are very common in evolutionary analyses, although they are often treated as incomplete data. Here, we provide statistical tools to analyze what we name "clade data," which are the ages of clades together with their numbers of species. We develop a general approach for the statistical modeling of variation in speciation and extinction rates, including temporal variation, unknown variation, and linear and nonlinear modeling. We show how this approach can be generalized to a wide range of situations, including testing the effects of life-history traits and environmental variables on diversification rates. We report the results of an extensive simulation study to assess the performance of some statistical tests presented here as well as of the estimators of speciation and extinction rates. These latter results suggest the possibility to estimate correctly extinction rate in the absence of fossils. An example with data on fish is presented. © 2013 The Author(s). Evolution © 2013 The Society for the Study of Evolution.

  1. Metal speciation: survey of environmental methods of analysis

    Energy Technology Data Exchange (ETDEWEB)

    Mach, M.H.; Nott, B.; Scott, J.W.; Maddalone, R.F.; Whiddon, N.T. [TRW, Redondo Beach, CA (United States). Chemistry Technology Dept.

    1996-07-01

    As part of a recent task under the EPRI Analytical Methods Qualification Program (RP 1851), TRW has surveyed the methods available for monitoring metal species in typical utility aqueous discharge streams. Methods for determining the individual species of these metals can become important in a regulatory sense as the EPA transitions to assessment of environmental risk based on bioavailability. For example, EPA considers methyl mercury and Cr(VI) much more toxic to the aquatic environment than inorganic mercury or Cr(III). The species of a given element can also differ in their transport and bioaccumulation. Methods for speciation generally include a selective separation step followed by standard metals analysis. Speciation, therefore, is mainly derived from the separation step and not from the method of final quantisation. Examples of separation/analysis include: selective extraction followed by graphite furnace atomic absorption or ICP-MS; separation by GC followed by metals detection; chelation and/or direct separation by LC followed by UV measurement or metals detection; and ion chromatography with conductivity, UV, or metals detection. There are a number of sampling issues associated with metal species such as stabilization (maintaining oxidation state), absorption, and filtration that need to be addressed in order to obtain and maintain a representative sample for analysis. 45 refs., 1 tab.

  2. Selenium speciation from food source to metabolites: a critical review

    Energy Technology Data Exchange (ETDEWEB)

    Dumont, Emmie; Vanhaecke, Frank; Cornelis, Rita [Ghent University, Department of Analytical Chemistry, Ghent (Belgium)

    2006-08-15

    Especially in the last decade, a vast number of papers on Se and its role in health issues have been published. This review gives a brief, critical overview of the main analytical findings reported in these papers. Of particular interest is the Se content in different food sources worldwide and the extent to which their consumption is reflected in the Se content of human tissues and body fluids. Several food sources, both natural (Brazil nuts, garlic, Brassica juncea) and Se-enriched (yeast-based supplements), are discussed as to origin, characteristics, Se metabolism and impact of their consumption on the human body. The continuous development of new and improvement of existing analytical techniques has provided different powerful tools to unravel the Se species and their function. An up-to-date literature study on Se speciation analysis is given, illustrating how analytical chemistry in its different facets aids in the identification of Se compounds and provides insight into the complete metabolic pathway of Se throughout the human body. This review includes a detailed image of the current state-of-the-art of Se speciation analysis in these food sources and in human tissues and body fluids. (orig.)

  3. Allopatric speciation within a cryptic species complex of Australasian octopuses.

    Science.gov (United States)

    Amor, Michael D; Norman, Mark D; Cameron, Hayley E; Strugnell, Jan M

    2014-01-01

    Despite extensive revisions over recent decades, the taxonomy of benthic octopuses (Family Octopodidae) remains in a considerable flux. Among groups of unresolved status is a species complex of morphologically similar shallow-water octopods from subtropical Australasia, including: Allopatric populations of Octopus tetricus on the eastern and western coasts of Australia, of which the Western Australian form is speculated to be a distinct or sub-species; and Octopus gibbsi from New Zealand, a proposed synonym of Australian forms. This study employed a combination of molecular and morphological techniques to resolve the taxonomic status of the 'tetricus complex'. Phylogenetic analyses (based on five mitochondrial genes: 12S rRNA, 16S rRNA, COI, COIII and Cytb) and Generalised Mixed Yule Coalescent (GMYC) analysis (based on COI, COIII and Cytb) distinguished eastern and Western Australian O. tetricus as distinct species, while O. gibbsi was found to be synonymous with the east Australian form (BS = >97, PP = 1; GMYC p = 0.01). Discrete morphological differences in mature male octopuses (based on sixteen morphological traits) provided further evidence of cryptic speciation between east (including New Zealand) and west coast populations; although females proved less useful in morphological distinction among members of the tetricus complex. In addition, phylogenetic analyses suggested populations of octopuses currently treated under the name Octopus vulgaris are paraphyletic; providing evidence of cryptic speciation among global populations of O. vulgaris, the most commercially valuable octopus species worldwide.

  4. Speciation and migration of 129I in soil profiles

    International Nuclear Information System (INIS)

    Luo, Maoyi; Hou, Xiaolin; Zhou, Weijian; He, Chaohui; Chen, Ning; Liu, Qi; Zhang, Luoyuan

    2013-01-01

    A method has been developed for speciation analysis of ultra low level 129 I in soil using sequential extraction combined with coprecipitation for separation of carrier free iodine and AMS measurement of 129 I. Two loess profiles collected from northwest China were analyzed for species of 129 I and 127 I. Similar partitioning of 129 I and 127 I was observed in the loess profiles, the distribution of iodine isotopes followed an order of organic > leachable > reducible > residue. The 129 I concentrations and 129 I/ 127 I ratios decreased exponentially with the depth, and 2 orders of magnitude lower in the deepest layer (60 and 90 cm) compared with the top layer, indicating a significant contribution of anthropogenic input in the upper layer, and high retention of 129 I in soil. The mobility of 129 I in different fractions decreased in an order of leachable > organic > oxides > residue. The results suggest that migration of iodine downwards in the soil profile is a slow process; the oxides and residue are the less mobile fractions of iodine. Highlights: ► 129 I concentration decreases exponentially with the depth of soil profile. ► The mobility of 129 I in fractions decreases: leachable > organic > oxides > residue. ► Iodine shows less mobility in oxides and residue fractions. ► High organic soil content can effectively reduce the migration of 129 I in the environment. ► Carrier free iodine AMS is an effective method for natural 129 I speciation analysis in the environment

  5. Allopatric Speciation within a Cryptic Species Complex of Australasian Octopuses

    Science.gov (United States)

    Amor, Michael D.; Norman, Mark D.; Cameron, Hayley E.; Strugnell, Jan M.

    2014-01-01

    Despite extensive revisions over recent decades, the taxonomy of benthic octopuses (Family Octopodidae) remains in a considerable flux. Among groups of unresolved status is a species complex of morphologically similar shallow-water octopods from subtropical Australasia, including: Allopatric populations of Octopus tetricus on the eastern and western coasts of Australia, of which the Western Australian form is speculated to be a distinct or sub-species; and Octopus gibbsi from New Zealand, a proposed synonym of Australian forms. This study employed a combination of molecular and morphological techniques to resolve the taxonomic status of the ‘tetricus complex’. Phylogenetic analyses (based on five mitochondrial genes: 12S rRNA, 16S rRNA, COI, COIII and Cytb) and Generalised Mixed Yule Coalescent (GMYC) analysis (based on COI, COIII and Cytb) distinguished eastern and Western Australian O. tetricus as distinct species, while O. gibbsi was found to be synonymous with the east Australian form (BS = >97, PP = 1; GMYC p = 0.01). Discrete morphological differences in mature male octopuses (based on sixteen morphological traits) provided further evidence of cryptic speciation between east (including New Zealand) and west coast populations; although females proved less useful in morphological distinction among members of the tetricus complex. In addition, phylogenetic analyses suggested populations of octopuses currently treated under the name Octopus vulgaris are paraphyletic; providing evidence of cryptic speciation among global populations of O. vulgaris, the most commercially valuable octopus species worldwide. PMID:24964133

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

    Energy Technology Data Exchange (ETDEWEB)

    Laudal, D.L.; Heidt, M.K. [Energy & Environmental Research Center, Grand Forks, ND (United States); Nott, B. [Electric Power Research Institute, Palo Alto, CA (United States)

    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.

  7. Assortative flocking in crossbills and implications for ecological speciation.

    Science.gov (United States)

    Smith, Julie W; Sjoberg, Stephanie M; Mueller, Matthew C; Benkman, Craig W

    2012-10-22

    How reproductive isolation is related to divergent natural selection is a central question in speciation. Here, we focus on several ecologically specialized taxa or 'call types' of red crossbills (Loxia curvirostra complex), one of the few groups of birds providing much evidence for ecological speciation. Call types differ in bill sizes and feeding capabilities, and also differ in vocalizations, such that contact calls provide information on crossbill phenotype. We found that two call types of red crossbills were more likely to approach playbacks of their own call type than those of heterotypics, and that their propensity to approach heterotypics decreased with increasing divergence in bill size. Although call similarity also decreased with increasing divergence in bill size, comparisons of responses to familiar versus unfamiliar call types indicate that the decrease in the propensity to approach heterotypics with increasing divergence in bill size was a learned response, and not a by-product of calls diverging pleiotropically as bill size diverged. Because crossbills choose mates while in flocks, assortative flocking could lead indirectly to assortative mating as a by-product. These patterns of association therefore provide a mechanism by which increasing divergent selection can lead to increasing reproductive isolation.

  8. AN ANALYTICAL METHOD FOR CHEMICAL SPECIATION OF SELENIUM IN SOIL

    Directory of Open Access Journals (Sweden)

    Constantin Luca

    2010-10-01

    Full Text Available Selenium is an essential microelement, sometimes redoubtable, through its beneficial role - risk depending on its concentration in the food chain, at low dose is an important nutrient in the life of humans and animals, contrary at high doses, it becomes toxic. Selenium may be find itself in the environment (soil, sediment, water in many forms (oxidized, reduced, organometallic which determine their mobility and toxicity. Determination of chemical speciation (identification of different chemical forms provides much more complete information for a better understanding of the behavior and the potential impact on the environment. In this work we present the results of methodological research on the extraction of sequential forms of selenium in the soil and the coupling of analytical methods capable of identifying very small amounts of selenium in soils An efficient scheme of sequential extractions forms of selenium (SES consisting in atomic absorption spectrometry coupled with hydride generation (HGAAS has been developed into five experimental steps, detailed in the paper. This operational scheme has been applied to the analysis of chemical speciation in the following areas: the Bărăgan Plain and Central Dobrogea of Romania.

  9. Technetium Inventory, Distribution, and Speciation in Hanford Tanks

    Energy Technology Data Exchange (ETDEWEB)

    Serne, R. Jeffrey [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rapko, Brian M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pegg, Ian L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2014-11-13

    The purpose of this report is three fold: 1) assemble the available information regarding Tc inventory, distribution between phases, and speciation in Hanford’s 177 storage tanks into a single, detailed, comprehensive assessment; 2) discuss the fate (distribution/speciation) of Tc once retrieved from the storage tanks and processed into final waste forms; and 3) discuss/document in less detail the available data on the inventory of Tc in other “pools” such as the vadose zone below inactive cribs and trenches, below single-shell tanks (SSTs) that have leaked, and in the groundwater below the Hanford Site. This report was revised in September 2014 to add detail and correct inaccuracies in Section 5.0 on the fate of technetium (Tc) recycle from the off-gas systems downstream of the low-activity waste (LAW) melters back to the melters, based on several reports that were not found in the original literature search on the topic. The newly provided reports, from experts active in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) glass studies, the Vitreous State Laboratory at The Catholic University of America (VSL) melter and off-gas system demonstrations and overall WTP systems analysis, were not originally found on electronic databases commonly searched. The major revisions to Section 5.0 also required changes to Section 7.0 (Summary and Conclusions) and this executive summary.

  10. Triassic-Jurassic pteridosperms of Australasia: speciation, diversity and decline

    Energy Technology Data Exchange (ETDEWEB)

    Pattemore, G. A.; Rigby, J. F.; Playford, G.

    2015-07-01

    Pteridosperms are preserved abundantly in the Gondwanan Triassic, with many species exhibiting consider- able morphological variation that has been attributed to a hybridization model of speciation. This is an improbable explanation given that hybridization is very rare in gymnosperms. Allopatric speciation resulting from geographic and climatic provincialism is a more likely explanation for the morphological diversity which is well represented in Anisian Norian (Middle and Upper Triassic) floras of Australasia and elsewhere in Gondwana. Most specimens are distributed among three families: Umkomasiaceae, Peltaspermaceae and Matatiellaceae. These families, together with other possibly pteridospermous genera, are reviewed herein. Diversity in these families apparently declined by the Rhaetian and they did not persist into the Gondwanan post-Triassic. Australasian post-Triassic strata contain remarkably different floral assemblages to those of the Triassic. No fructifications are clearly pteridospermous and no remains show any obvious relationship with pteridosperms of the Gondwanan Triassic. Caytonialean fructifications are not known in Australasian strata; however, associated foliage has been reported from the Eastern Gondwanan Upper Triassic through Middle Jurassic including Australia. Much fern-like foliage, claimed to be pteridospermous from the Lower Jurassic through Eocene of Eastern Gondwana, lacks supporting evidence of such affiliation. (Author)

  11. Flow Injection Photochemical Vapor Generation Coupled with Miniaturized Solution-Cathode Glow Discharge Atomic Emission Spectrometry for Determination and Speciation Analysis of Mercury.

    Science.gov (United States)

    Mo, Jiamei; Li, Qing; Guo, Xiaohong; Zhang, Guoxia; Wang, Zheng

    2017-10-03

    A novel, compact, and green method was developed for the determination and speciation analysis of mercury, based on flow injection photochemical vapor generation (PVG) coupled with miniaturized solution cathode glow discharge-atomic emission spectroscopy (SCGD-AES). The SCGD was generated between a miniature hollow titanium tube and a solution emerging from a glass capillary. Cold mercury vapor (Hg(0)) was generated by PVG and subsequently delivered to the SCGD for excitation, and finally the emission signals were recorded by a miniaturized spectrograph. The detection limits (DLs) of Hg(II) and methylmercury (MeHg) were both determined to be 0.2 μg L -1 . Moreover, mercury speciation analysis could also be performed by using different wavelengths and powers from the UV lamp and irradiation times. Both Hg(II) and MeHg can be converted to Hg(0) for the determination of total mercury (T-Hg) with 8 W/254 nm UV lamp and 60 s irradiation time; while only Hg(II) can be reduced to Hg(0) and determined selectively with 4 W/365 nm UV lamp and 20 s irradiation time. Then, the concentration of MeHg can be calculated by subtracting the Hg(II) from the T-Hg. Because of its similar sensitivity and DL at 8 W/254 nm, the simpler and less toxic Hg(II) was used successfully as a primary standard for the quantification of T-Hg. The novel PVG-SCGD-AES system provides not only a 365-fold improvement in the DL for Hg(II) but also a nonchromatographic method for the speciation analysis of mercury. After validating its accuracy, this method was successfully used for mercury speciation analysis of water and biological samples.

  12. [Molecular biology, darwinism and nomogenesis].

    Science.gov (United States)

    Vol'kenshteĭn, M V

    1987-01-01

    The theory of nomogenesis put forward by L. S. Berg in 1922 is discussed. It is shown that side by side with some erroneous anti-darwinian ideas the theory contains a series of important suggestions which anticipate the further development of the synthetic theory of evolution. Berg has foreseen the development of molecular biology. Thus he was the fore-teller of our branch of science. The theory of nomogenesis emphasized the limitations of natural selection which determine the directionality of evolution. Berg treated the speciation as a kind of phase transition. Even the most conscientious critics of Berg have misrepresented the real sense of his works. It is totally groundless to treat nomogenesis as an idealistic of Lamarkian theory. Berg was superior to his critics. However the enthusiasm about nomogenesis in our time shows the inability to separate "the grains from weeds".

  13. A review on speciation of iodine-129 in the environmental and biological samples

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Hansen, Violeta; Aldahan, Ala

    2009-01-01

    As a long-lived beta-emitting radioisotope of iodine, I-129 is produced both naturally and as a result of human nuclear activities. At present time, the main part of I-129 in the environment originates from the human nuclear activity, especially the releases from the spent nuclear fuel reprocessi...

  14. Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals.

    Science.gov (United States)

    Stockdale, Anthony; Tipping, Edward; Lofts, Stephen; Mortimer, Robert J G

    2016-02-16

    Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

  15. Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

    Science.gov (United States)

    Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

    2017-12-01

    Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

  16. Speciation and Distribution of Trace Metals and Organic Matter in Marine Lake as In Situ Laboratory

    Science.gov (United States)

    Mlakar, M.; Fiket, Ž.; Cuculić, V.; Cukrov, N.; Geček, S.

    2016-02-01

    Marine lakes are unique, isolated marine systems, also recognized as in situ "laboratories" in which geochemical processes on a different scale compared to the open sea, can be observed. Impact of organic matter cycling on distribution of trace metals in the marine lake Mir, located on Dugi Otok Island, in the central part of the eastern Adriatic Sea, was investigated. Intense spatial and seasonal variations of physico-chemical parameters and organic matter concentrations in the water column of the Lake are governed predominantly by natural processes. Enhanced oxygen consumption in the Lake during summer season, high organic carbon concentrations and low redox potential result in occasional occurrence of anoxic conditions in the bottom layers. Speciation modelling showed that dissolved trace metals Cu, Pb and Zn, are mostly bound to organic matter, while Cd, Co and Ni are present predominantly as free ions and inorganic complexes. Trace metals removal from the water column and their retention in the sediment was found to depend on the nature of the relationship between specific metal and high proportion of organic matter (up to 9%) and inorganic phases, Fe-oxyhydroxydes or biogenic calcite. Surrounding karstic background, with occasional occurrences of red soil characterize deposited sediments as coarse grained and carbonate rich, whose elemental composition is affected by bathymetry of the basin and overall biological production.

  17. Estimating parameters of speciation models based on refined summaries of the joint site-frequency spectrum.

    Directory of Open Access Journals (Sweden)

    Aurélien Tellier

    Full Text Available Understanding the processes and conditions under which populations diverge to give rise to distinct species is a central question in evolutionary biology. Since recently diverged populations have high levels of shared polymorphisms, it is challenging to distinguish between recent divergence with no (or very low inter-population gene flow and older splitting events with subsequent gene flow. Recently published methods to infer speciation parameters under the isolation-migration framework are based on summarizing polymorphism data at multiple loci in two species using the joint site-frequency spectrum (JSFS. We have developed two improvements of these methods based on a more extensive use of the JSFS classes of polymorphisms for species with high intra-locus recombination rates. First, using a likelihood based method, we demonstrate that taking into account low-frequency polymorphisms shared between species significantly improves the joint estimation of the divergence time and gene flow between species. Second, we introduce a local linear regression algorithm that considerably reduces the computational time and allows for the estimation of unequal rates of gene flow between species. We also investigate which summary statistics from the JSFS allow the greatest estimation accuracy for divergence time and migration rates for low (around 10 and high (around 100 numbers of loci. Focusing on cases with low numbers of loci and high intra-locus recombination rates we show that our methods for the estimation of divergence time and migration rates are more precise than existing approaches.

  18. Mathematical treatment of isotopologue and isotopomer speciation and fractionation in biochemical kinetics

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2010-03-01

    We present a mathematical treatment of the kinetic equations that describe isotopologue and isotopomer speciation and fractionation during enzyme-catalyzed biochemical reactions. These equations, presented here with the name GEBIK (general equations for biochemical isotope kinetics) and GEBIF (general equations for biochemical isotope fractionation), take into account microbial biomass and enzyme dynamics, reaction stoichiometry, isotope substitution number, and isotope location within each isotopologue and isotopomer. In addition to solving the complete GEBIK and GEBIF, we also present and discuss two approximations to the full solutions under the assumption of biomass-free and enzyme steady-state, and under the quasi-steady-state assumption as applied to the complexation rate. The complete and approximate approaches are applied to observations of biological denitrification in soils. Our analysis highlights that the full GEBIK and GEBIF provide a more accurate description of concentrations and isotopic compositions of substrates and products throughout the reaction than do the approximate forms. We demonstrate that the isotopic effects of a biochemical reaction depend, in the most general case, on substrate and complex concentrations and, therefore, the fractionation factor is a function of time. We also demonstrate that inverse isotopic effects can occur for values of the fractionation factor smaller than 1, and that reactions that do not discriminate isotopes do not necessarily imply a fractionation factor equal to 1.

  19. Trace cobalt speciation in bacteria and at enzymic active sites using emission Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kamnev, A.A.; Antonyuk, L.P.; Smirnova, V.E.; Serebrennikova, O.B. [Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, Saratov (Russian Federation); Kulikov, L.A.; Perfiliev, Yu.D. [Laboratory of Nuclear Chemistry Techniques, Department of Radiochemistry, Faculty of Chemistry, Moscow State University (Russian Federation)

    2002-02-01

    {sup 57}Co emission Moessbauer spectroscopy (EMS) allows the chemical state of cobalt, as influenced by its coordination environment, to be monitored in biological samples at its physiological (trace) concentrations. To draw attention to EMS as a valuable tool for speciation of cobalt in biocomplexes, the process of cobalt(II) metabolism in cells of the plant growth-promoting rhizobacterium Azospirillum brasilense Sp245 was investigated using EMS of {sup 57}Co{sup II}-doped bacterial cells. EMS measurements also showed {sup 57}Co{sup II}-activated glutamine synthetase (GS, a key enzyme of nitrogen metabolism, isolated from this bacterium) to have two different cobalt(II) forms at its active sites, in agreement with data available on other bacterial GSs. Chemical after-effects following electron capture by the nucleus of the parent {sup 57}Co{sup II} during the {sup 57}Co{yields}{sup 57}Fe transition, which contribute to the formation of a stabilised daughter {sup 57}Fe{sup III} component along with the nucleogenic {sup 57}Fe{sup II} forms, are also briefly considered. (orig.)

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

    Science.gov (United States)

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

    2017-09-01

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

  1. A multi-technique investigation of copper and zinc distribution, speciation and potential bioavailability in biosolids

    International Nuclear Information System (INIS)

    Donner, E.; Ryan, C.G.; Howard, D.L.; Zarcinas, B.; Scheckel, K.G.; McGrath, S.P.; Jonge, M.D. de; Paterson, D.; Naidu, R.; Lombi, E.

    2012-01-01

    The use of biosolids in agriculture continues to be debated, largely in relation to their metal contents. Our knowledge regarding the speciation and bioavailability of biosolids metals is still far from complete. In this study, a multi-technique approach was used to investigate copper and zinc speciation and partitioning in one contemporary and two historical biosolids used extensively in previous research and field trials. Using wet chemistry and synchrotron spectroscopy techniques it was shown that copper/zinc speciation in the biosolids was largely equivalent despite the biosolids being derived from different countries over a 50 year period. Furthermore, copper speciation was consistently dominated by sorption to organic matter whereas Zn partitioned mainly to iron oxides. These data suggest that the results of historical field trials are still relevant for modern biosolids and that further risk assessment studies should concentrate particularly on Cu as this metal is associated with the mineralisable biosolids fraction. - Highlights: ► Complementary techniques were used to investigate Cu and Zn speciation in biosolids. ► Historic and contemporary biosolids with differing metal contents were examined. ► Similarities in Cu/Zn speciation were observed irrespective of biosolids provenance. ► Key binding environments identified were organic matter for Cu and Fe oxides for Zn. ► Similarities show historic field trial results are still relevant for biosolids management. - Historic and contemporary biosolids show similarities in Cu/Zn speciation despite having very different total Zn/Cu contents.

  2. Airborne Vertical Profiling of Mercury Speciation near Tullahoma, TN, USA

    Directory of Open Access Journals (Sweden)

    Steve Brooks

    2014-08-01

    Full Text Available Atmospheric transport and in situ oxidation are important factors influencing mercury concentrations at the surface and wet and dry deposition rates. Contributions of both natural and anthropogenic processes can significantly impact burdens of mercury on local, regional and global scales. To address these key issues in atmospheric mercury research, airborne measurements of mercury speciation and ancillary parameters were conducted over a region near Tullahoma, Tennessee, USA, from August 2012 to June 2013. Here, for the first time, we present vertical profiles of Hg speciation from aircraft for an annual cycle over the same location. These airborne measurements included gaseous elemental mercury (GEM, gaseous oxidized mercury (GOM and particulate bound mercury (PBM, as well as ozone (O3, sulfur dioxide (SO2, condensation nuclei (CN and meteorological parameters. The flights, each lasting ~3 h, were conducted typically one week out of each month to characterize seasonality in mercury concentrations. Data obtained from 0 to 6 km altitudes show that GEM exhibited a relatively constant vertical profile for all seasons with an average concentration of 1.38 ± 0.17 ng∙m−3. A pronounced seasonality of GOM was observed, with the highest GOM concentrations up to 120 pg∙m−3 in the summer flights and lowest (0–20 pg∙m−3 in the winter flights. Vertical profiles of GOM show the maximum levels at altitudes between 2 and 4 km. Limited PBM measurements exhibit similar levels to GOM at all altitudes. HYSPLIT back trajectories showed that the trajectories for elevated GOM (>70 pg∙m−3 or PBM concentrations (>30 pg∙m−3 were largely associated with air masses coming from west/northwest, while events with low GOM (<20 pg∙m−3 or PBM concentrations (<5 pg∙m−3 were generally associated with winds from a wider range of wind directions. This is the first set of speciated mercury vertical profiles collected in a single location over the course

  3. Speciated Elemental and Isotopic Characterization of Atmospheric Aerosols - Recent Advances

    Science.gov (United States)

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

    2007-12-01

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

  4. Selenium speciation influences bioaccumulation in Limnodynastes peronii tadpoles

    Energy Technology Data Exchange (ETDEWEB)

    Lanctôt, C.M., E-mail: c.lanctot@griffith.edu.au [Central Queensland University, School of Medical and Applied Sciences, Gladstone, QLD 4680 (Australia); Australian Rivers Institute, School of Environment, Griffith University, Southport, QLD 4215 (Australia); Melvin, S.D., E-mail: s.melvin@griffith.edu.au [Australian Rivers Institute, School of Environment, Griffith University, Southport, QLD 4215 (Australia); Cresswell, T., E-mail: tom.cresswell@ansto.gov.au [Australian Nuclear Science and Technology Organisation (ANSTO), Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)

    2017-06-15

    Highlights: • Differences in SeIV and SeVI bioaccumulation and biodistribution were assessed. • Limnodynastes peronii tadpoles accumulated more selenite than selenate. • Selenium depuration kinetics was similar for both forms. • Tadpoles accumulated Se predominantly in the digestive and excretory organs. - Abstract: Despite being essential for animal health and fitness, Se has a relatively narrow range between deficiency and toxicity, and excess Se can cause a variety of adverse effects in aquatic organisms. Amphibians are particularly vulnerable to contaminants during larval aquatic life stage, because they can accumulate toxic ions through various routes including skin, gills, lungs and digestive tract. Few attempts have been made to understand the tissue-specific accumulation of trace elements, including the impacts of chemical speciation in developing amphibian larvae. We used radiolabelled {sup 75}Se to explore the biokinetics and tissue distributions of the two dominant forms occurring in surface waters, selenite (SeIV) and selenate (SeVI). Tadpoles of the native Australian frog Limnodynastes peronii were exposed to Se in both forms, and live-animal gamma spectroscopy was used to track accumulation and retention over time. Tissue biodistributions were also quantified at the end of the uptake and depuration phases. Results showed the bioconcentration of SeIV to be 3 times greater compared to SeVI, but rates of elimination were similar for both forms. This suggests a change of Se speciation within the organism prior to excretion. Depuration kinetics were best described by a one-phase exponential decay model, and tadpoles retained approximately 19% of the accumulated Se after 12 days of depuration in clean water. Selenium bioaccumulation was greatest in digestive and excretory organs, as well as the eye, which may directly relate to previously reported Se-induced impairments. Results demonstrate how the use of radiotracing techniques can significantly

  5. Speciation and bioavailability of lead in complementary medicines

    International Nuclear Information System (INIS)

    Bolan, S.; Naidu, R.; Kunhikrishnan, A.; Seshadri, B.; Ok, Y.S.; Palanisami, T.; Dong, M.; Clark, I.

    2016-01-01

    Complementary medicines have associated risks which include toxic heavy metal(loid) and pesticide contamination. The objective of this study was to examine the speciation and bioavailability of lead (Pb) in selected complementary medicines. Six herbal and six ayurvedic medicines were analysed for: (i) total heavy metal(loid) contents including arsenic (As), cadmium (Cd), Pb and mercury (Hg); (ii) speciation of Pb using sequential fractionation and extended x-ray absorption fine structure (EXAFS) techniques; and (iii) bioavailability of Pb using a physiologically-based in vitro extraction test (PBET). The daily intake of Pb through the uptake of these medicines was compared with the safety guidelines for Pb. The results indicated that generally ayurvedic medicines contained higher levels of heavy metal(loid)s than herbal medicines with the amount of Pb much higher than the other metal(loid)s. Sequential fractionation indicated that while organic-bound Pb species dominated the herbal medicines, inorganic-bound Pb species dominated the ayurvedic medicines. EXAFS data indicated the presence of various Pb species in ayurvedic medicines. This implies that Pb is derived from plant uptake and inorganic mineral input in herbal and ayurvedic medicines, respectively. Bioavailability of Pb was higher in ayurvedic than herbal medicines, indicating that Pb added as a mineral therapeutic input is more bioavailable than that derived from plant uptake. There was a positive relationship between soluble Pb fraction and bioavailability indicating that solubility is an important factor controlling bioavailability. The daily intake values for Pb as estimated by total and bioavailable metal(loid) contents are likely to exceed the safe threshold level in certain ayurvedic medicines. This research demonstrated that Pb toxicity is likely to result from the regular intake of these medicines which requires further investigation. - Highlights: • Pb species in complementary medicines was

  6. Speciation of mercury in fish samples by flow injection catalytic cold vapour atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Yanlin [NanoScience and Sensor Technology Research Group, School of Applied Sciences and Engineering, Monash University, Churchill, Victoria 3842 (Australia); Adeloju, Samuel B., E-mail: Sam.Adeloju@monash.edu [NanoScience and Sensor Technology Research Group, School of Applied Sciences and Engineering, Monash University, Churchill, Victoria 3842 (Australia)

    2012-04-06

    Highlights: Black-Right-Pointing-Pointer Successful speciation of inorganic and organic Hg with Fe{sup 3+}, Cu{sup 2+} and thiourea as catalysts. Black-Right-Pointing-Pointer Best sensitivity enhancement and similar sensitivity for MeHg and Hg{sup 2+} with Fe{sup 3+}. Black-Right-Pointing-Pointer Successful use of Hg{sup 2+} as the primary standard for quantification of inorganic and total-Hg. Black-Right-Pointing-Pointer Quantitative extraction of Hg and MeHg with 2 M HCl which contained thiourea. Black-Right-Pointing-Pointer Integration with FIA for rapid analysis with a sample throughput of 180 h{sup -1}. - Abstract: A rapid flow injection catalytic cold vapour atomic absorption spectrometric (FI-CCV-AAS) method is described for speciation and determination of mercury in biological samples. Varying concentrations of NaBH{sub 4} were employed for mercury vapour generation from inorganic and mixture of inorganic and organic (total) Hg. The presence of Fe{sup 3+}, Cu{sup 2+} and thiourea had catalytic effect on mercury vapour generation from methylmercury (MeHg) and, when together, Cu{sup 2+} and thiourea had synergistic catalytic effect on the vapour generation. Of the two metal ions, Fe{sup 3+} gave the best sensitivity enhancement, achieving the same sensitivity for MeHg and inorganic Hg{sup 2+}. Due to similarity of resulting sensitivity, Hg{sup 2+} was used successfully as a primary standard for quantification of inorganic and total Hg. The catalysis was homogeneous in nature, and it was assumed that the breaking of the C-Hg bond was facilitated by the delocalization of the 5d electron pairs in Hg atom. The extraction of MeHg and inorganic mercury (In-Hg) in fish samples were achieved quantitatively with hydrochloric acid in the presence of thiourea and determined by FI-CCV-AAS. The application of the method to the quantification of mercury species in a fish liver reference material DOLT-4 gave 91.5% and 102.3% recoveries for total and methyl mercury

  7. Arsenic speciation by X-ray spectroscopy using resonant Raman Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, H.J.; Leani, J.J. [Universidad Nacional de Cordoba, Cba (Argentina); Perez, C.A. [Laboratorio Nacional de Luz Sincrotron (LNLS), Campinas, SP (Brazil)

    2012-07-01

    Full text: The toxicity of arsenic species is widely known. A realistic evaluation of the risk posed by As depends on accurate determination of As speciation, because its toxicity and mobility varies with oxidation state and chemical environment. The most toxic species are inorganic As (III) and As (V) called respectively arsenite or trivalent arsenic, and arsenate or pentavalent arsenic. Recently, x-ray Resonant Raman Scattering spectroscopy has been successfully employed to determine the oxidation state of metals. In this work we use RRS spectroscopy to perform arsenic speciation. The measurements were carried out in XRF station of the D09B-XRF beamline at the Brazilian synchrotron facility (LNLS, Campinas). Mineral samples of As in different oxidation states (As(III) and AS(V)), and two biological forms of arsenic (monomethylarsonic acid (MMA(V) and dimethylarsinic acid DMA(V)) were analysed. The samples were diluted, deposited on silicon wafers and allowed to dry. The amount of liquid deposited on the reflector before evaporation was 20 microliters for all the specimens. These samples were irradiated with monochromatic photons of 11816 eV, i.e., below the K-edge of arsenic in order to inspect the Raman emissions. The measuring lifetime was 3600 sec for each sample. Spectra were analysed with specific programs for spectrum analysis using non-conventional functions for data fitting, i.e., modified Voight functions (for Compton peaks), Gaussian functions for fluorescent and for low intensity peaks (such as escape peaks and other contributions), and polynomial functions for the background. Raman peaks were fitted using specific functions. In this work we have shown that resonant Raman scattering spectroscopy can be used to analyse arsenic species. The method is very simple and reliable. The most important feature of this method relies in the possibility of using the same spectrometer of XRF analysis or TXRF analysis. In this way, practically in the same experiment

  8. Speciation of mercury in fish samples by flow injection catalytic cold vapour atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Zhang Yanlin; Adeloju, Samuel B.

    2012-01-01

    Highlights: ► Successful speciation of inorganic and organic Hg with Fe 3+ , Cu 2+ and thiourea as catalysts. ► Best sensitivity enhancement and similar sensitivity for MeHg and Hg 2+ with Fe 3+ . ► Successful use of Hg 2+ as the primary standard for quantification of inorganic and total-Hg. ► Quantitative extraction of Hg and MeHg with 2 M HCl which contained thiourea. ► Integration with FIA for rapid analysis with a sample throughput of 180 h −1 . - Abstract: A rapid flow injection catalytic cold vapour atomic absorption spectrometric (FI-CCV-AAS) method is described for speciation and determination of mercury in biological samples. Varying concentrations of NaBH 4 were employed for mercury vapour generation from inorganic and mixture of inorganic and organic (total) Hg. The presence of Fe 3+ , Cu 2+ and thiourea had catalytic effect on mercury vapour generation from methylmercury (MeHg) and, when together, Cu 2+ and thiourea had synergistic catalytic effect on the vapour generation. Of the two metal ions, Fe 3+ gave the best sensitivity enhancement, achieving the same sensitivity for MeHg and inorganic Hg 2+ . Due to similarity of resulting sensitivity, Hg 2+ was used successfully as a primary standard for quantification of inorganic and total Hg. The catalysis was homogeneous in nature, and it was assumed that the breaking of the C-Hg bond was facilitated by the delocalization of the 5d electron pairs in Hg atom. The extraction of MeHg and inorganic mercury (In-Hg) in fish samples were achieved quantitatively with hydrochloric acid in the presence of thiourea and determined by FI-CCV-AAS. The application of the method to the quantification of mercury species in a fish liver reference material DOLT-4 gave 91.5% and 102.3% recoveries for total and methyl mercury, respectively. The use of flow injection enabled rapid analysis with a sample throughput of 180 h −1 .

  9. The speciation of dissolved elements in aquatic solution. Radium and actinides

    International Nuclear Information System (INIS)

    Haesaenen, E.

    1994-01-01

    In the publication, the chemistry and speciation of radium, thorium, protactinium, uranium, neptunium, lutonium, americium and curium in ground-water environment is reviewed. Special attention is given to the transuranium elements, which have a central role in the repository of nuclear wastes. The most important methods used in the speciation of these elements is presented. The laser-induced methods, developed in the 1980's, are especially discussed. These have made it possible, e.g., to speciate the transuranium elements in their very low, actual repository ground-water concentrations (10-100 ng/l). (54 refs., 10 figs., 3 tabs.)

  10. Speciation and solubility of neptunium in underground environments by paper electrophoresis

    International Nuclear Information System (INIS)

    Nagasaki, S.; Tanaka, Satoru; Takahashi, Yoichi

    1988-01-01

    Speciation and solubility of neptunium were studied using paper electrophoresis, ion exchange and ultrafiltration. Among these methods, the paper electrophoresis was found to be suitable for measuring speciation and solubility of neptunium of low concentration, if chemical species had opposite charge to each other or dissolved species had a charge. Using paper electrophoresis, hydrolysis constants of NpO 2 OH 0 and NpO 2 - (OH) 2 - and solubility product of NpO 2 were obtained and ionic-strength dependence of speciation was observed. (author) 9 refs.; 3 figs.; 2 tabs

  11. Paradigms in isotope dilution mass spectrometry for elemental speciation analysis

    International Nuclear Information System (INIS)

    Meija, Juris; Mester, Zoltan

    2008-01-01

    Isotope dilution mass spectrometry currently stands out as the method providing results with unchallenged precision and accuracy in elemental speciation. However, recent history of isotope dilution mass spectrometry has shown that the extent to which this primary ratio measurement method can deliver accurate results is still subject of active research. In this review, we will summarize the fundamental prerequisites behind isotope dilution mass spectrometry and discuss their practical limits of validity and effects on the accuracy of the obtained results. This review is not to be viewed as a critique of isotope dilution; rather its purpose is to highlight the lesser studied aspects that will ensure and elevate current supremacy of the results obtained from this method

  12. Speciation and antibiotic susceptibility patterns of coagulase-negative staphylococci.

    Science.gov (United States)

    Smith, D J; Kaplan, R L; Landau, W; Trenholme, G M

    1982-08-01

    During a six month period, 191 isolates of coagulase-negative staphylococci from blood, urine, cerebrospinal fluid and heart valves were identified to species level and tested for antimicrobial susceptibility. Seventy-one percent of isolates were Staphylococcus epidermidis, 8% Staphylococcus warneri, 7% Staphylococcus hominis, 7% Staphylococcus haemolyticus, 4% Staphylococcus capitis, 2% Staphylococcus saprophyticus and 1% Staphylococcus cohnii. Approximately 4% of isolates were felt to be associated with infection. Overall, 18% of isolates were susceptible to penicillin G, 61% oxacillin, 98% cephalothin, 98% cefamandole, 72% cefotaxime, 95% cefsulodin, 76% gentamicin, 64% clindamycin and 98% rifampicin. All isolates were susceptible to vancomycin. Vancomycin, rifampicin, cephalothin and cefamandole showed excellent activity against oxacillin-resistant isolates. With one exception, speciation was not helpful in determining whether or not an isolate was associated with infection.

  13. Towards a common thermodynamic database for speciation models

    International Nuclear Information System (INIS)

    Lee, J. van der; Lomenech, C.

    2004-01-01

    Bio-geochemical speciation models and reactive transport models are reaching an operational stage, allowing simulation of complex dynamic experiments and description of field observations. For decades, the main focus has been on model performance but at present, the availability and reliability of thermodynamic data is the limiting factor of the models. Thermodynamic models applied to real and complex geochemical systems require much more extended thermodynamic databases with many minerals, colloidal phases, humic and fulvic acids, cementitious phases and (dissolved) organic complexing agents. Here we propose a methodological approach to achieve, ultimately, a common, operational database including the reactions and constants of these phases. Provided they are coherent with the general thermodynamic laws, sorption reactions are included as well. We therefore focus on sorption reactions and parameter values associated with specific sorption models. The case of sorption on goethite has been used to illustrate the way the methodology handles the problem of inconsistency and data quality. (orig.)

  14. Some actinide speciation using laser induced photoacoustic spectroscopy

    International Nuclear Information System (INIS)

    Pollard, P.M.; McMillan, J.W.; Phillips, G.; Thomason, H.P.; Ewart, F.T.

    1988-01-01

    Laser induced photoacoustic spectroscopy is an attractive method for the speciation of actinides in solutions from nuclear disposal studies because it is essentially non-invasive and has a reasonably high sensitivity, down to ca 10 -8 M. A novel true dual beam system has been constructed and commissioned at Harwell with a performance at least equal to any others in existence. It is based on a XeCl excimer laser and a dye laser, beam splitter, two laser power monitors and photoacoustic cells. The wavelength scanning, data collection, and spectra processing and display are controlled by an Apricot computer. The sample and reference cells are housed in an inert atmosphere glove box. Early applications of the equipment described include measurements of Am and Np species under varying conditions of pH, Eh and carbonate concentration. The observations show some correlation with predictions made using the geochemical modelling code PHREEQE. (orig.)

  15. Arsenic speciation in solids using X-ray absorption spectroscopy

    Science.gov (United States)

    Foster, Andrea L.; Kim, Chris S.

    2014-01-01

    Synchrotron-based X-ray absorption spectroscopy (XAS) is an in situ, minimally-destructive, element-specific, molecular-scale structural probe that has been employed to study the chemical forms (species) of arsenic (As) in solid and aqueous phases (including rocks, soils, sediment, synthetic compounds, and numerous types of biota including humans) for more than 20 years. Although several excellent reviews of As geochemistry and As speciation in the environment have been published previously (including recent contributions in this volume), the explosion of As-XAS studies over the past decade (especially studies employing microfocused X-ray beams) warrants this new review of the literature and of data analysis methods.

  16. Chemval project report on stage 1: verification of speciation models

    International Nuclear Information System (INIS)

    Read, D.; Broyd, T.W.

    1989-01-01

    CHEMVAL is an international geochemical exercise, which aims at applicating and validating predictive computer programmes describing the chemistry of radionuclides in the geosphere. As a component of the CEC project MIRAGE- second phase (on migration of radionuclides in the geosphere), CHEMVAL is carried out in the framework of the third community R and D programme of radioactive waste management and storage. The present report is the first of a series devoted to the verification and validation of aqueous speciation and coupled chemical transport codes. Five cases systems are studied, namely, cement, clay, sandstore, granite and limestone. Overall, good agreement was obtained. Reasons for divergence in results have been explored and recommendations are made at the appropriate stages for enhancement of the thermodynamic data base. A listing of the preliminary CHEMVAL Project Data Base is provided

  17. The Development of Molybdenum Speciation as a Paleoredox Tool

    Science.gov (United States)

    Rodley, J.; Peacock, C.; Mosselmans, J. F. W.; Poulton, S.

    2017-12-01

    The redox state of the oceans has changed throughout geological time and an understanding of these changes is essential to elucidate links between ocean chemistry, climate and life. Due to its abundance in seawater and redox-sensitive nature, molybdenum has enormous potential as a paleoredox proxy. Although a significant amount of research has been done on molybdenum in ancient and modern sediments in terms of its concentrations and isotopic ratios there remains a limited understanding of the drawdown mechanisms of molybdenum under different redox conditions restricting its use in identifying a range of redox states. In order to address these uncertainties, we have developed a novel sequential extraction technique to examine molybdenum concentrations in six sediment fractions from modern samples that represent oxic, nitrogenous, ferruginous and euxinic environments. In addition we use µ-XRF and µ-XANES synchrotron spectroscopy to examine the molybdenum speciation within these fractions and environments. To interpret our µ-XANES data we have developed an extensive library of molybdenum XANES standards that represent molybdenum sequestration by the sediment fractions identified from the sequential extraction. To further verify our synchrotron results we developed a series of µ-XANES micro-column experiments to examine preferential uptake pathways of molybdenum to different sediment phases under a euxinic water column. The initial data from both the sequential extraction and µ-XANES methods indicate that molybdenum is not limited to a single burial pathway in any of the redox environments. We find that each of the redox environments can be characterised by a limited set of molybdenum phase associations, with molybdenum adsorption to pyrite likely the dominant burial pathway. These findings agree with existing research for molybdenum speciation in euxinic environments suggesting that both pyrite and sulphidised organic matter act as important molybdenum sinks. Our

  18. Field Deployable Method for Arsenic Speciation in Water.

    Science.gov (United States)

    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

  19. Hydrogen speciation in hydrated layers on nuclear waste glass

    International Nuclear Information System (INIS)

    Aines, R.D.; Weed, H.C.; Bates, J.K.

    1987-01-01

    The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 and 165, and PNL 76-68), which were leached at 90 0 C (all glasses) or hydrated in a vapor-saturated atmosphere at 202 0 C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was found in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 μm layer on SRL-131 glass formed by leaching at 90 0 C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H + interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups

  20. Technetium Inventory, Distribution, and Speciation in Hanford Tanks

    Energy Technology Data Exchange (ETDEWEB)

    Serne, R. Jeffrey; Rapko, Brian M.

    2014-05-02

    The purpose of this report is three fold: 1) assemble the available information regarding technetium (Tc) inventory, distribution between phases, and speciation in Hanford’s 177 storage tanks into a single, detailed, comprehensive assessment; 2) discuss the fate (distribution/speciation) of Tc once retrieved from the storage tanks and processed into a final waste form; and 3) discuss/document in less detail the available data on the inventory of Tc in other "pools" such as the vadose zone below inactive cribs and trenches, below single-shell tanks (SSTs) that have leaked, and in the groundwater below the Hanford Site. A thorough understanding of the inventory for mobile contaminants is key to any performance or risk assessment for Hanford Site facilities because potential groundwater and river contamination levels are proportional to the amount of contaminants disposed at the Hanford Site. Because the majority of the total 99Tc produced at Hanford (~32,600 Ci) is currently stored in Hanford’s 177 tanks (~26,500 Ci), there is a critical need for knowledge of the fate of this 99Tc as it is removed from the tanks and processed into a final solid waste form. Current flow sheets for the Hanford Waste Treatment and Immobilization Plant process show most of the 99Tc will be immobilized as low-activity waste glass that will remain on the Hanford Site and disposed at the Integrated Disposal Facility (IDF); only a small fraction will be shipped to a geologic repository with the immobilized high-level waste. Past performance assessment studies, which focused on groundwater protection, have shown that 99Tc would be the primary dose contributor to the IDF performance.

  1. Speciation with gene flow in equids despite extensive chromosomal plasticity.

    Science.gov (United States)

    Jónsson, Hákon; Schubert, Mikkel; Seguin-Orlando, Andaine; Ginolhac, Aurélien; Petersen, Lillian; Fumagalli, Matteo; Albrechtsen, Anders; Petersen, Bent; Korneliussen, Thorfinn S; Vilstrup, Julia T; Lear, Teri; Myka, Jennifer Leigh; Lundquist, Judith; Miller, Donald C; Alfarhan, Ahmed H; Alquraishi, Saleh A; Al-Rasheid, Khaled A S; Stagegaard, Julia; Strauss, Günter; Bertelsen, Mads Frost; Sicheritz-Ponten, Thomas; Antczak, Douglas F; Bailey, Ernest; Nielsen, Rasmus; Willerslev, Eske; Orlando, Ludovic

    2014-12-30

    Horses, asses, and zebras belong to a single genus, Equus, which emerged 4.0-4.5 Mya. Although the equine fossil record represents a textbook example of evolution, the succession of events that gave rise to the diversity of species existing today remains unclear. Here we present six genomes from each living species of asses and zebras. This completes the set of genomes available for all extant species in the genus, which was hitherto represented only by the horse and the domestic donkey. In addition, we used a museum specimen to characterize the genome of the quagga zebra, which was driven to extinction in the early 1900s. We scan the genomes for lineage-specific adaptations and identify 48 genes that have evolved under positive selection and are involved in olfaction, immune response, development, locomotion, and behavior. Our extensive genome dataset reveals a highly dynamic demographic history with synchronous expansions and collapses on different continents during the last 400 ky after major climatic events. We show that the earliest speciation occurred with gene flow in Northern America, and that the ancestor of present-day asses and zebras dispersed into the Old World 2.1-3.4 Mya. Strikingly, we also find evidence for gene flow involving three contemporary equine species despite chromosomal numbers varying from 16 pairs to 31 pairs. These findings challenge the claim that the accumulation of chromosomal rearrangements drive complete reproductive isolation, and promote equids as a fundamental model for understanding the interplay between chromosomal structure, gene flow, and, ultimately, speciation.

  2. Phosphorous Speciation in WTR-treated Biosolids Using XANES

    Science.gov (United States)

    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.

  3. Chromium speciation in solid matrices and regulation: a review

    Energy Technology Data Exchange (ETDEWEB)

    Unceta, N. [University of the Basque Country, Department of Analytical Chemistry, Faculty of Pharmacy, Vitoria-Gasteiz (Spain); Seby, F. [Ultra Traces Analyses Aquitaine (UT2A), Helioparc Pau-Pyrenees, Pau (France); Malherbe, J.; Donard, O.F.X. [Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, IPREM, UMR CNRS 5254, Pau (France)

    2010-06-15

    In recent years, the extensive use of chromium in industrial processes has led to the promotion of several directives and recommendations by the European Union, that try to limit and regulate the presence of Cr(VI) in the environment and to protect industrial workers using chromium and end-users of manufactured products. As a consequence, new standard methods and analytical procedures have been published at the EU level for Cr(VI) determination in soil, sludge, sediment, and similar waste materials, workplace atmospheres, cement, packaging materials, industrially produced samples, and corrosion-protection layers on some components of vehicles and electrical and electronic equipment. The objective of this article is to summarize the different directives and recommendations and to critically review the currently existing standard methods and the methods published in the literature for chromium speciation in the above mentioned solid matrices, putting the emphasis on the different extraction procedures which have been developed for each matrix. Particular attention has been paid to Cr(III) and Cr(VI) inter-conversions that can occur during extraction and efforts to minimize these unwanted reactions. Although the use of NaOH-Na{sub 2}CO{sub 3} solutions with hot plate extraction seems to be the more widespread procedure, species transformation can still occur and several studies suggest that speciated isotope-dilution mass spectrometry (SIDMS) could be a suitable tool for correction of these interconversions. Besides, recent studies have proved the role of Cr(III) in chromium toxicology. As a consequence, the authors suggest an update of standard methods in the near future. (orig.)

  4. Mercury speciation during in situ thermal desorption in soil

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chang Min, E-mail: cmpark80@gmail.com; Katz, Lynn E.; Liljestrand, Howard M.

    2015-12-30

    Highlights: • Impact of soil conditions on distribution and phase transitions of Hg was identified. • Metallic Hg was slowly transformed to Hg{sup 0} gas until the temperature reached 358.15 K. • Phase change of HgCl{sub 2(s)} completely occurred without decomposition at 335.15 K. • HgS remained solid in dry soil sharply decreased in the narrow temperature range. • Hg gas can be easily captured with higher vapor pressures of soil compositions. - Abstract: Metallic mercury (Hg{sup 0}) and its compounds are highly mobile and toxic environmental pollutants at trace level. In situ thermal desorption (ISTD) is one of the soil remediation processes applying heat and vacuum simultaneously. Knowledge of thermodynamic mercury speciation is imperative to understand the fate and transport of mercury during thermal remediation and operate the treatment processes in a cost-effective manner. Hence, speciation model for inorganic mercury was developed over a range of environmental conditions to identify distribution of dissolved mercury species and potential transformations of mercury at near source environment. Simulation of phase transitions for metallic mercury, mercury(II) chloride and mercury sulfide with temperature increase showed that complete vaporization of metallic mercury and mercury(II) chloride were achieved below the boiling point of water. The effect of soil compositions on mercury removal was also evaluated to better understand thermal remediation process. Higher vapor pressures expected both from soil pore water and inorganic carbonate minerals in soil as well as creation of permeability were significant for complete vaporization and removal of mercury.

  5. Mercury speciation during in situ thermal desorption in soil

    International Nuclear Information System (INIS)

    Park, Chang Min; Katz, Lynn E.; Liljestrand, Howard M.

    2015-01-01

    Highlights: • Impact of soil conditions on distribution and phase transitions of Hg was identified. • Metallic Hg was slowly transformed to Hg"0 gas until the temperature reached 358.15 K. • Phase change of HgCl_2_(_s_) completely occurred without decomposition at 335.15 K. • HgS remained solid in dry soil sharply decreased in the narrow temperature range. • Hg gas can be easily captured with higher vapor pressures of soil compositions. - Abstract: Metallic mercury (Hg"0) and its compounds are highly mobile and toxic environmental pollutants at trace level. In situ thermal desorption (ISTD) is one of the soil remediation processes applying heat and vacuum simultaneously. Knowledge of thermodynamic mercury speciation is imperative to understand the fate and transport of mercury during thermal remediation and operate the treatment processes in a cost-effective manner. Hence, speciation model for inorganic mercury was developed over a range of environmental conditions to identify distribution of dissolved mercury species and potential transformations of mercury at near source environment. Simulation of phase transitions for metallic mercury, mercury(II) chloride and mercury sulfide with temperature increase showed that complete vaporization of metallic mercury and mercury(II) chloride were achieved below the boiling point of water. The effect of soil compositions on mercury removal was also evaluated to better understand thermal remediation process. Higher vapor pressures expected both from soil pore water and inorganic carbonate minerals in soil as well as creation of permeability were significant for complete vaporization and removal of mercury.

  6. Trace and ultratrace level elemental and speciation analysis

    International Nuclear Information System (INIS)

    Arunachalam, J.

    2012-01-01

    Accurate determination of elements present at parts per million and billion levels in various matrices is a growing requirement in different fields. In environmental sciences various trace elements need to be analyzed so as establish the dispersal models of pollutants or the adequacy of effluent treatment prior to discharge into water bodies. The issues of bioaccumulation and magnification are important in aquatic systems. In nutrition and biochemistry one has to establish the bio-availability of essential and toxic elemental species as toxic elements prevent assimilation of essential elements. Fission and fusion technologies use a variety of structural materials requiring many trace elements to be present at levels strictly below the specified levels. Ultra-pure bulk semiconductor materials are required for fabrication devices. In metallurgy and materials sciences too, various trace elements are known to influence the properties. In the emerging fields like nanotechnology, it is necessary to understand the passage and accumulation of nano-particles inside the cells, through trace analysis. Many analytical techniques exist which can provide the concentration information in the bulk materials with good accuracy. They include ICP-AES, FAAS, and ICP-MS, which are solution based techniques. Direct solid state analytical techniques are Glow Discharge Mass Spectrometry (GDMS) and XRF. Accelerator based ion-beam analysis techniques can provide information on concentration and depth profiles of different elements in layered structures. Hyphenated techniques such as HPLC/lC-ICPMS, are helpful in identifying various chemical oxidation states in which a given element might be present in a matrix, which is termed as speciation analysis. This presentation will include the existing analytical competencies and the laboratory requirements for trace and ultra trace element elemental and speciation analyses and their applications. (author)

  7. Modelling interaction of deep groundwaters with bentonite and radionuclide speciation

    International Nuclear Information System (INIS)

    Wanner, H.

    1986-04-01

    In the safety analysis recently reported for a potential Swiss high-level waste repository, radionuclide speciation and solubility limits are calculated for expected granitic groundwater conditions. With the objective of deriving a more realistic description of radionuclide release from the near-field, an investigation has been initiated to quantitatively specify the chemistry of the near-field. In the Swiss case, the main components of the near-field are the glass waste-matrix, a thick steel canister horizontally emplaced in a drift, and a backfill of highly compacted sodium bentonite. This report describes a thermodynamic model which is used to estimate the chemical composition of the pore water in compacted sodium bentonite. Solubility limits and speciation of important actinides and the fission product technetium in the bentonite pore water are then calculated. The model is based on available experimental data on the interaction of sodium bentonite and groundwater and represents means of extrapolation from laboratory data to repository conditions. The basic reactions between sodium bentonite and groundwater are described by an ion-exchange model for sodium, potassium, magnesium, and calcium. The model assumes equilibrium with calcite as long as sufficient carbonates remain in the bentonite, as well as quartz saturation. It is calculated that the pore water of compacted sodium bentonite saturated with Swiss Reference Groundwater will have a pH value of 9.7 and a free carbonate activity of 8x10 -4 M. The long-term situation is modelled by the assumption that the near-field of a deep repository behaves like a mixing tank. In this way, an attempt is made to account for the continuous water exchange between the near-field and the host rock. It is found that sodium bentonite will be slowly converted to calcium bentonite. This conversion is roughly estimated to be completed after 2 million years

  8. Selenium Speciation and Management in Wet FGD Systems

    Energy Technology Data Exchange (ETDEWEB)

    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

  9. Modern Biology

    OpenAIRE

    ALEKSIC, Branko

    2014-01-01

    The purpose of this course is to learn the philosophy, principles, and techniques of modern biology. The course is particularly designed for those who have not learned biology previously or whose major is other than biology, and who may think that they do not need to know any biology at all. The topics are covered in a rather general, overview manner, but certain level of diligence in grasping concepts and memorizing the terminology is expected.

  10. Influence of natural organic matter on the speciation of radionuclides in a geochemistry context; Influence de la matiere organique naturelle sur la speciation des radionucleides en contexte geochimique

    Energy Technology Data Exchange (ETDEWEB)

    Marang, L

    2007-09-15

    The principal aim of this work is the study of the influence of natural organic matter, in particularly humic substances (HS), on the speciation of radionuclides (RN). The studied radionuclides are cobalt (II), europium (III) and uranium (VI). It has been shown that mobility and bioavailability of a metal are related to its speciation. The NICA-Donnan model describes metal ion binding to NOM: it accounts for NOM chemical heterogeneity, competition during binding and ionic strength effects. However the model has been calibrated with a limited number of experimental data for the RN. Indeed there is only a few speciation technique available for the study of the interactions RN-HS. Within the framework of this study, we have developed and optimised speciation technique (Flux Donnan Membrane Technique and the use of an un-solubilized humic acid) in order to acquire new experimental data, we have also studied the effect of the competition on RN speciation and finally we have tested the model capacity to predict the RN behavior in laboratory or in situ. (author)

  11. Speciation on oceanic islands: rapid adaptive divergence vs. cryptic speciation in a Guadalupe Island songbird (Aves: Junco.

    Directory of Open Access Journals (Sweden)

    Pau Aleixandre

    Full Text Available The evolutionary divergence of island populations, and in particular the tempo and relative importance of neutral and selective factors, is of central interest to the study of speciation. The rate of phenotypic evolution upon island colonization can vary greatly among taxa, and cases of convergent evolution can further confound the inference of correct evolutionary histories. Given the potential lability of phenotypic characters, molecular dating of insular lineages analyzed in a phylogenetic framework provides a critical tool to test hypotheses of phenotypic divergence since colonization. The Guadalupe junco is the only insular form of the polymorphic dark-eyed junco (Junco hyemalis, and shares eye and plumage color with continental morphs, yet presents an enlarged bill and reduced body size. Here we use variation in mtDNA sequence, morphological traits and song variables to test whether the Guadalupe junco evolved rapidly following a recent colonization by a mainland form of the dark-eyed junco, or instead represents a well-differentiated "cryptic" lineage adapted to the insular environment through long-term isolation, with plumage coloration a result of evolutionary convergence. We found high mtDNA divergence of the island lineage with respect to both continental J. hyemalis and J. phaeonotus, representing a history of isolation of about 600,000 years. The island lineage was also significantly differentiated in morphological and male song variables. Moreover, and contrary to predictions regarding diversity loss on small oceanic islands, we document relatively high levels of both haplotypic and song-unit diversity on Guadalupe Island despite long-term isolation in a very small geographic area. In contrast to prevailing taxonomy, the Guadalupe junco is an old, well-differentiated evolutionary lineage, whose similarity to mainland juncos in plumage and eye color is due to evolutionary convergence. Our findings confirm the role of remote islands

  12. Speciation on oceanic islands: rapid adaptive divergence vs. cryptic speciation in a Guadalupe Island songbird (Aves: Junco).

    Science.gov (United States)

    Aleixandre, Pau; Hernández Montoya, Julio; Milá, Borja

    2013-01-01

    The evolutionary divergence of island populations, and in particular the tempo and relative importance of neutral and selective factors, is of central interest to the study of speciation. The rate of phenotypic evolution upon island colonization can vary greatly among taxa, and cases of convergent evolution can further confound the inference of correct evolutionary histories. Given the potential lability of phenotypic characters, molecular dating of insular lineages analyzed in a phylogenetic framework provides a critical tool to test hypotheses of phenotypic divergence since colonization. The Guadalupe junco is the only insular form of the polymorphic dark-eyed junco (Junco hyemalis), and shares eye and plumage color with continental morphs, yet presents an enlarged bill and reduced body size. Here we use variation in mtDNA sequence, morphological traits and song variables to test whether the Guadalupe junco evolved rapidly following a recent colonization by a mainland form of the dark-eyed junco, or instead represents a well-differentiated "cryptic" lineage adapted to the insular environment through long-term isolation, with plumage coloration a result of evolutionary convergence. We found high mtDNA divergence of the island lineage with respect to both continental J. hyemalis and J. phaeonotus, representing a history of isolation of about 600,000 years. The island lineage was also significantly differentiated in morphological and male song variables. Moreover, and contrary to predictions regarding diversity loss on small oceanic islands, we document relatively high levels of both haplotypic and song-unit diversity on Guadalupe Island despite long-term isolation in a very small geographic area. In contrast to prevailing taxonomy, the Guadalupe junco is an old, well-differentiated evolutionary lineage, whose similarity to mainland juncos in plumage and eye color is due to evolutionary convergence. Our findings confirm the role of remote islands in driving

  13. Quantitative uranium speciation with U M{sub 4,5}-edge HERFD absorption spectra

    Energy Technology Data Exchange (ETDEWEB)

    Kvashnina, Kristina O.; Rossberg, Andre [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures

    2017-06-01

    This report gives a brief description of the quantitative uranium speciation performed by iterative transformation factor analysis (ITFA) of High Energy Resolution X-ray Fluorescence Detection (HERFD) data collected at the M{sub 4,5} edge.

  14. Data Fusion approach for spatial analysis of speciated PM2.5 across time

    Data.gov (United States)

    U.S. Environmental Protection Agency — speciated pm2.5 monitoring data and total pm2.5 monitoring data. This dataset is associated with the following publication: Rundel, C., E. Schliep, A. Gelfand, and...

  15. Current mass spectrometry strategies for selenium speciation in dietary sources of high-selenium

    Energy Technology Data Exchange (ETDEWEB)

    Infante, Heidi Goenaga; Hearn, Ruth; Catterick, Tim [LGC Limited, Teddington, Middlesex (United Kingdom)

    2005-06-01

    This document reviews the most relevant mass spectrometry approaches to selenium (Se) speciation in high-Se food supplements in terms of qualitative and quantitative Se speciation and Se-containing species identification, with special reference to high-Se yeast, garlic, onions and Brazil nuts. Important topics such as complexity of Se speciation in these materials and the importance of combining Se-specific detection and molecule-specific determination of the particular species of this element in parallel with chromatography, to understand their nutritional role and cancer preventive properties are critically discussed throughout. The versatility and potential of mass spectrometric detection in this field are clearly demonstrated. Although great advances have been achieved, further developments are required, especially if ''speciated''certified reference materials (CRMs) are to be produced for validation of measurements of target Se-containing species in Se-food supplements. (orig.)

  16. Biodiesel and Cold Temperature Effects on Speciated Mobile Source Air Toxics from Modern Diesel Trucks

    Science.gov (United States)

    Speciated volatile organic compounds (VOCs) with a particular focus on mobile source air toxics (MSATs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a temperature controlled chass...

  17. Biodiesel and Cold Temperature Effect on Speciated Mobile Source Air Toxics from Modern Diesel Trucks

    Science.gov (United States)

    Speciated volatile organic compounds (VOCs) with a particular focus on mobile source air toxics (MSATs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a temperature controlled chass...

  18. Genomic islands of divergence are not affected by geography of speciation in sunflowers.

    Science.gov (United States)

    Renaut, S; Grassa, C J; Yeaman, S; Moyers, B T; Lai, Z; Kane, N C; Bowers, J E; Burke, J M; Rieseberg, L H

    2013-01-01

    Genomic studies of speciation often report the presence of highly differentiated genomic regions interspersed within a milieu of weakly diverged loci. The formation of these speciation islands is generally attributed to reduced inter-population gene flow near loci under divergent selection, but few studies have critically evaluated this hypothesis. Here, we report on transcriptome scans among four recently diverged pairs of sunflower (Helianthus) species that vary in the geographical context of speciation. We find that genetic divergence is lower in sympatric and parapatric comparisons, consistent with a role for gene flow in eroding neutral differences. However, genomic islands of divergence are numerous and small in all comparisons, and contrary to expectations, island number and size are not significantly affected by levels of interspecific gene flow. Rather, island formation is strongly associated with reduced recombination rates. Overall, our results indicate that the functional architecture of genomes plays a larger role in shaping genomic divergence than does the geography of speciation.

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

    Science.gov (United States)

    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.

  20. Depletive stripping chronopotentiometry : a major step forward in electrochemical stripping techniques for metal ion speciation analysis

    NARCIS (Netherlands)

    Town, R.M.; Leeuwen, van H.P.

    2004-01-01

    A comparative evaluation of the utility of the various modes of stripping chronopotentiometry (SCP) for trace metal speciation analysis is presented in the broad context of stripping voltammetric techniques. The remarkable fundamental advantages of depletive SCP at scanned deposition potential

  1. Mathematical biology

    CERN Document Server

    Murray, James D

    1993-01-01

    The book is a textbook (with many exercises) giving an in-depth account of the practical use of mathematical modelling in the biomedical sciences. The mathematical level required is generally not high and the emphasis is on what is required to solve the real biological problem. The subject matter is drawn, e.g. from population biology, reaction kinetics, biological oscillators and switches, Belousov-Zhabotinskii reaction, reaction-diffusion theory, biological wave phenomena, central pattern generators, neural models, spread of epidemics, mechanochemical theory of biological pattern formation and importance in evolution. Most of the models are based on real biological problems and the predictions and explanations offered as a direct result of mathematical analysis of the models are important aspects of the book. The aim is to provide a thorough training in practical mathematical biology and to show how exciting and novel mathematical challenges arise from a genuine interdisciplinary involvement with the biosci...

  2. Phosphorus Speciation of Forest-soil Organic Surface Layers using P K-edge XANES Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    J Prietzel; J Thieme; D Paterson

    2011-12-31

    The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water-logging (Stagnosol, Rheic Histosol) was analyzed by P K-edge XANES and subsequent Linear Combination Fitting. In both soils, {approx}70% of the P was inorganic phosphate and {approx}30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water-logging in the Histosol compared to the Stagnosol did not affect P speciation.

  3. Speciation, diversification, and coexistence of sessile species that compete for space

    DEFF Research Database (Denmark)

    Mitarai, Namiko; Heinsalu, Els; Sneppen, Kim

    2014-01-01

    Speciation, diversification, and competition between species challenge the stability of complex ecosystems. Laboratory experiments often focus on one or two species competing under conditions where they may grow exponentially. Field studies, in contrast, emphasize multi-species communities...... appear due to immigration from outside of the considered ecosystem. The species self-organize their spatial distribution through competitive interactions to create many patches, implicitly protecting each other from competitively superior species, and speciation in each patch leads the system to high...

  4. Arsenic speciation by liquid chromatography coupled with ionspray tandem mass spectrometry

    DEFF Research Database (Denmark)

    Corr, J. J.; Larsen, Erik Huusfeldt

    1996-01-01

    Ionspray mass spectrometry, a well established organic analysis technique, has been coupled to high-performance liquid chromatography for speciation of organic arsenic compounds, The ionspray source and differentially pumped interface of the mass spectrometer were operated in dual modes...... fragmentation patterns showing molecular dissociation through an expected common product ion were obtained for the four arsenosugars, Molecular mode detection was utilized for qualitative verification of speciation analysis by high-performance liquid chromatography coupled to inductively coupled plasma mass...

  5. The shape and temporal dynamics of phylogenetic trees arising from geographic speciation.

    Science.gov (United States)

    Pigot, Alex L; Phillimore, Albert B; Owens, Ian P F; Orme, C David L

    2010-12-01

    Phylogenetic trees often depart from the expectations of stochastic models, exhibiting imbalance in diversification among lineages and slowdowns in the rate of lineage accumulation through time. Such departures have led to a widespread perception that ecological differences among species or adaptation and subsequent niche filling are required to explain patterns of diversification. However, a key element missing from models of diversification is the geographical context of speciation and extinction. In this study, we develop a spatially explicit model of geographic range evolution and cladogenesis, where speciation arises via vicariance or peripatry, and explore the effects of these processes on patterns of diversification. We compare the results with those observed in 41 reconstructed avian trees. Our model shows that nonconstant rates of speciation and extinction are emergent properties of the apportioning of geographic ranges that accompanies speciation. The dynamics of diversification exhibit wide variation, depending on the mode of speciation, tendency for range expansion, and rate of range evolution. By varying these parameters, the model is able to capture many, but not all, of the features exhibited by birth-death trees and extant bird clades. Under scenarios with relatively stable geographic ranges, strong slowdowns in diversification rates are produced, with faster rates of range dynamics leading to constant or accelerating rates of apparent diversification. A peripatric model of speciation with stable ranges also generates highly unbalanced trees typical of bird phylogenies but fails to produce realistic range size distributions among the extant species. Results most similar to those of a birth-death process are reached under a peripatric speciation scenario with highly volatile range dynamics. Taken together, our results demonstrate that considering the geographical context of speciation and extinction provides a more conservative null model of

  6. Adaptive divergence with gene flow in incipient speciation of Miscanthus floridulus / sinensis complex (Poaceae)

    KAUST Repository

    Huang, Chao-Li; Ho, Chuan-Wen; Chiang, Yu-Chung; Shigemoto, Yasumasa; Hsu, Tsai-Wen; Hwang, Chi-Chuan; Ge, Xue-Jun; Chen, Charles; Wu, Tai-Han; Chou, Chang-Hung; Huang, Hao-Jen; Gojobori, Takashi; Osada, Naoki; Chiang, Tzen-Yuh

    2014-01-01

    Young incipient species provide ideal materials for untangling the process of ecological speciation in the presence of gene flow. The Miscanthus floridulus/sinensis complex exhibits diverse phenotypic and ecological differences despite recent divergence (approximately 1.59million years ago). To elucidate the process of genetic differentiation during early stages of ecological speciation, we analyzed genomic divergence in the Miscanthus complex using 72 randomly selected genes from a newly assembled transcriptome. In this study, rampant gene flow was detected between species, estimated as M=3.36x10(-9) to 1.20x10(-6), resulting in contradicting phylogenies across loci. Nevertheless, beast analyses revealed the species identity and the effects of extrinsic cohesive forces that counteracted the non-stop introgression. As expected, early in speciation with gene flow, only 3-13 loci were highly diverged; two to five outliers (approximately 2.78-6.94% of the genome) were characterized by strong linkage disequilibrium, and asymmetrically distributed among ecotypes, indicating footprints of diversifying selection. In conclusion, ecological speciation of incipient species of Miscanthus probably followed the parapatric model, whereas allopatric speciation cannot be completely ruled out, especially between the geographically isolated northern and southern M.sinensis, for which no significant gene flow across oceanic barriers was detected. Divergence between local ecotypes in early-stage speciation began at a few genomic regions under the influence of natural selection and divergence hitchhiking that overcame gene flow.

  7. Geological and climatic forces driving speciation in the continentally distributed trilling chorus frogs (Pseudacris).

    Science.gov (United States)

    Lemmon, Emily Moriarty; Lemmon, Alan R; Cannatella, David C

    2007-09-01

    Tertiary geological events and Quaternary climatic fluctuations have been proposed as important factors of speciation in the North American flora and fauna. Few studies, however, have rigorously tested hypotheses regarding the specific factors driving divergence of taxa. Here, we test explicit speciation hypotheses by correlating geologic events with divergence times among species in the continentally distributed trilling chorus frogs (Pseudacris). In particular, we ask whether marine inundation of the Mississippi Embayment, uplift of the Appalachian Mountains, or modification of the ancient Teays-Mahomet River system contributed to speciation. To examine the plausibility of ancient rivers causing divergence, we tested whether modern river systems inhibit gene flow. Additionally, we compared the effects of Quaternary climatic factors (glaciation and aridification) on levels of genetic variation. Divergence time estimates using penalized likelihood and coalescent approaches indicate that the major lineages of chorus frogs diversified during the Tertiary, and also exclude Quaternary climate change as a factor in speciation of chorus frogs. We show the first evidence that inundation of the Mississippi Embayment contributed to speciation. We reject the hypotheses that Cenozoic uplift of the Appalachians and that diversion of the Teays-Mahomet River contributed to speciation in this clade. We find that by reducing gene flow, rivers have the potential to cause divergence of lineages. Finally, we demonstrate that populations in areas affected by Quaternary glaciation and aridification have reduced levels of genetic variation compared to those from more equable regions, suggesting recent colonization.

  8. Hybridization masks speciation in the evolutionary history of the Galápagos marine iguana.

    Science.gov (United States)

    MacLeod, Amy; Rodríguez, Ariel; Vences, Miguel; Orozco-terWengel, Pablo; García, Carolina; Trillmich, Fritz; Gentile, Gabriele; Caccone, Adalgisa; Quezada, Galo; Steinfartz, Sebastian

    2015-06-22

    The effects of the direct interaction between hybridization and speciation-two major contrasting evolutionary processes--are poorly understood. We present here the evolutionary history of the Galápagos marine iguana (Amblyrhynchus cristatus) and reveal a case of incipient within--island speciation, which is paralleled by between-island hybridization. In-depth genome-wide analyses suggest that Amblyrhynchus diverged from its sister group, the Galápagos land iguanas, around 4.5 million years ago (Ma), but divergence among extant populations is exceedingly young (less than 50,000 years). Despite Amblyrhynchus appearing as a single long-branch species phylogenetically, we find strong population structure between islands, and one case of incipient speciation of sister lineages within the same island--ostensibly initiated by volcanic events. Hybridization between both lineages is exceedingly rare, yet frequent hybridization with migrants from nearby islands is evident. The contemporary snapshot provided by highly variable markers indicates that speciation events may have occurred throughout the evolutionary history of marine iguanas, though these events are not visible in the deeper phylogenetic trees. We hypothesize that the observed interplay of speciation and hybridization might be a mechanism by which local adaptations, generated by incipient speciation, can be absorbed into a common gene pool, thereby enhancing the evolutionary potential of the species as a whole. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  9. Adaptive divergence with gene flow in incipient speciation of Miscanthus floridulus / sinensis complex (Poaceae)

    KAUST Repository

    Huang, Chao-Li

    2014-11-11

    Young incipient species provide ideal materials for untangling the process of ecological speciation in the presence of gene flow. The Miscanthus floridulus/sinensis complex exhibits diverse phenotypic and ecological differences despite recent divergence (approximately 1.59million years ago). To elucidate the process of genetic differentiation during early stages of ecological speciation, we analyzed genomic divergence in the Miscanthus complex using 72 randomly selected genes from a newly assembled transcriptome. In this study, rampant gene flow was detected between species, estimated as M=3.36x10(-9) to 1.20x10(-6), resulting in contradicting phylogenies across loci. Nevertheless, beast analyses revealed the species identity and the effects of extrinsic cohesive forces that counteracted the non-stop introgression. As expected, early in speciation with gene flow, only 3-13 loci were highly diverged; two to five outliers (approximately 2.78-6.94% of the genome) were characterized by strong linkage disequilibrium, and asymmetrically distributed among ecotypes, indicating footprints of diversifying selection. In conclusion, ecological speciation of incipient species of Miscanthus probably followed the parapatric model, whereas allopatric speciation cannot be completely ruled out, especially between the geographically isolated northern and southern M.sinensis, for which no significant gene flow across oceanic barriers was detected. Divergence between local ecotypes in early-stage speciation began at a few genomic regions under the influence of natural selection and divergence hitchhiking that overcame gene flow.

  10. Host-symbiont co-speciation and reductive genome evolution in gut symbiotic bacteria of acanthosomatid stinkbugs

    Directory of Open Access Journals (Sweden)

    Kamagata Yoichi

    2009-01-01

    Full Text Available Abstract Background Host-symbiont co-speciation and reductive genome evolution have been commonly observed among obligate endocellular insect symbionts, while such examples have rarely been identified among extracellular ones, the only case reported being from gut symbiotic bacteria of stinkbugs of the family Plataspidae. Considering that gut symbiotic communities are vulnerable to invasion of foreign microbes, gut symbiotic associations have been thought to be evolutionarily not stable. Stinkbugs of the family Acanthosomatidae harbor a bacterial symbiont in the midgut crypts, the lumen of which is completely sealed off from the midgut main tract, thereby retaining the symbiont in the isolated cryptic cavities. We investigated histological, ecological, phylogenetic, and genomic aspects of the unique gut symbiosis of the acanthosomatid stinkbugs. Results Phylogenetic analyses showed that the acanthosomatid symbionts constitute a distinct clade in the γ-Proteobacteria, whose sister groups are the obligate endocellular symbionts of aphids Buchnera and the obligate gut symbionts of plataspid stinkbugs Ishikawaella. In addition to the midgut crypts, the symbionts were located in a pair of peculiar lubricating organs associated with the female ovipositor, by which the symbionts are vertically transmitted via egg surface contamination. The symbionts were detected not from ovaries but from deposited eggs, and surface sterilization of eggs resulted in symbiont-free hatchlings. The symbiont-free insects suffered retarded growth, high mortality, and abnormal morphology, suggesting important biological roles of the symbiont for the host insects. The symbiont phylogeny was generally concordant with the host phylogeny, indicating host-symbiont co-speciation over evolutionary time despite the extracellular association. Meanwhile, some local host-symbiont phylogenetic discrepancies were found, suggesting occasional horizontal symbiont transfers across the host

  11. Speciation of plutonium during sorption and diffusion in Opalinus clay

    International Nuclear Information System (INIS)

    Kaplan, Ugras

    2013-01-01

    The presented work was carried out in the framework of the BMWi-project ''Interaction and migration of actinides in natural clay rocks taking into account humic substances and clay organic matter - Interactions of neptunium and plutonium with natural clay rocks''. For the long-term safety assessments of nuclear repositories, the possible migration of the radiotoxic wastes into the environment must be considered. Due to its long half-life (T 1/2 = 24000 y) 239 Pu has a significant contribution to the radiotoxicity of spent nuclear fuel in a repository after long periods of storage. The redox-sensitive plutonium has a very complicated chemical behavior. In aqueous solution under environmental relevant conditions Pu can exist in oxidation states +III to +VI and it can exist in up to four oxidation states simultaneously in a solution. Clays are considered as a possible host rock formation for of high-level radioactive waste disposal. Therefore, detailed information on the mobilization and immobilization of plutonium through / into the groundwater from a repository are of special interest. In this work new insights into the interaction between Pu and natural Opalinus clay (OPA, Mont Terri, Switzerland) are obtained with regard to the disposal of heat-generating radioactive waste in a deep geological repository.rnThe focus of this work was on the determination of the speciation of Pu on the mineral surface after sorption and diffusion process by different synchrotron based techniques (μ-XRF, μ-XANES/-EXAFS, μ-XRD, and EXAFS/XANES). The interaction between Pu and OPA was studied in batch sorption and diffusion experiments in dependence of various experimental parameters (e.g. pH, Pu oxidation state). Sorption experiments showed that some experimental parameters (e.g. temperature, humic acid) have a significant impact on the sorption of Pu on OPA. Speciation studies were performed as a function of various chemical parameters on powder samples form batch experiments as

  12. INORGANIC ARSENIC SPECIATION IN THE ATMOSPHERE: STUDY IN ISFAHAN

    Directory of Open Access Journals (Sweden)

    A KALANTARI

    2000-06-01

    Full Text Available Introduction. Arsenic is one of the most hazardous elements that associate with airborne particulate matter in the atmosphere. Among the different species of arsenic, ASIII has the most toxic and carcinogenic property between any other kind of this element. Arsenic speciation is important in environmental studies. Methods. We collected 59 samples of airborne particulate matter from the atmosphere in Isfahan in a three months period by a high volume air sampler with a flow rate of 1 m3 min-1. Air particulates were collected on the paper filter (Whatman No.41. Four different digestive procedures were examined in order to find the best method. At last we chose digestion of filter with HCI (10-4N due to its feasibility, cost benefit and efficacy. Other methods that examined were digestion of filter with a mixture of HN03 and H2O2, with a mixture of HNO3 and H2O2 and with HCI (1 N. The determination of As3+ and As5+ concentrations were performed by hydrIde generation atomic absorption spectrometry. The effect of Ph on the absorption signal was also investigated in arsenic speciation. Results. Average of total saspended particles (TSP in July, August, and September 1998 were 223, 172, and 247 mg.m3 respectively. The recovery of arsenic from airborne particulate matter was almost the same for the different digestion methods. The concentration and volume of NaBH4 was optimized for determining of different species of arsenic. At pH=5, Asv didn't produce any absorption signal. So, the determination of ASm was carried out easilyat the above mentioned pH. The concentrations of total arsenic were determined in 47 samples. The mean concentrations of total arsenic in July, August and September were 3.31, 2.01 and 2.6, respectively. Discussion. More than 50 percent of total atmospheric arsenic exists as ASIII which is the most toxic and carcinogenic forms of this element. So, it is recommended to make a suitable policy for decreasing of this hazardous

  13. High resolution microprofiling, fractionation and speciation at sediment water interfaces

    Science.gov (United States)

    Fabricius, Anne-Lena; Duester, Lars; Ecker, Dennis; Ternes, Thomas A.

    2016-04-01

    Within aquatic environments, the exchange between the sediment and the overlaying water is often driven by steep gradients of, e.g., the oxygen concentration, the redox potential or the pH value at the sediment water interface (SWI). Important transport processes at the SWI are sedimentation and resuspension of particulate matter and diffusional fluxes of dissolved substances. To gain a better understanding of the key factors and processes determining the fate of substances at the SWI, methods with a spatial high resolution are required that enable the investigation of several sediment parameters in parallel to different analytes of interest in the sediment pore water. Moreover, beside the total content, questions concerning the speciation and fractionation are of concern in studying the different (transport) processes. Due to the availability of numerous micro-sensors and -electrodes (e.g., O2, redox potential, pH value, H2S, N2O) and the development of methods for pore water sampling [1], the toolbox to study the heterogeneous and often dynamic conditions at the SWI at a sub-millimetre scale were considerably improved. Nevertheless, the methods available for pore water sampling often require the installation of the sampling devices at the sampling site and/or intensive preparation procedures that may influence the conditions at the area studied and/or the characteristics of the samples taken. By combination of a micro profiling system with a new micro filtration probe head connected to a pump and a fraction collector, a micro profiling and micro sampling system ("missy") was developed that enables for the first time a direct, automate and low invasive sampling of small volumes (content of metal(loid)s, but also their fractionation (size dependent and micelle mediated) or speciation related distributions along sediment depth profiles in parallel to different sediment parameters (O2, redox and pH). Together with the results of missy-experiments, the results of

  14. Speciated arsenic in air: measurement methodology and risk assessment considerations.

    Science.gov (United States)

    Lewis, Ari S; Reid, Kim R; Pollock, Margaret C; Campleman, Sharan L

    2012-01-01

    Accurate measurement of arsenic (As) in air is critical to providing a more robust understanding of arsenic exposures and associated human health risks. Although there is extensive information available on total arsenic in air, less is known on the relative contribution of each arsenic species. To address this data gap, the authors conducted an in-depth review of available information on speciated arsenic in air. The evaluation included the type of species measured and the relative abundance, as well as an analysis of the limitations of current analytical methods. Despite inherent differences in the procedures, most techniques effectively separated arsenic species in the air samples. Common analytical techniques such as inductively coupled plasma mass spectrometry (ICP-MS) and/or hydride generation (HG)- or quartz furnace (GF)-atomic absorption spectrometry (AAS) were used for arsenic measurement in the extracts, and provided some of the most sensitive detection limits. The current analysis demonstrated that, despite limited comparability among studies due to differences in seasonal factors, study duration, sample collection methods, and analytical methods, research conducted to date is adequate to show that arsenic in air is mainly in the inorganic form. Reported average concentrations of As(III) and As(V) ranged up to 7.4 and 10.4 ng/m3, respectively, with As(V) being more prevalent than As(III) in most studies. Concentrations of the organic methylated arsenic compounds are negligible (in the pg/m3 range). However because of the variability in study methods and measurement methodology, the authors were unable to determine the variation in arsenic composition as a function of source or particulate matter (PM) fraction. In this work, the authors include the implications of arsenic speciation in air on potential exposure and risks. The authors conclude that it is important to synchronize sample collection, preparation, and analytical techniques in order to generate

  15. Trichoderma inoculation augments grain amino acids and mineral nutrients by modulating arsenic speciation and accumulation in chickpea (Cicer arietinum L.).

    Science.gov (United States)

    Tripathi, Pratibha; Singh, Poonam C; Mishra, Aradhana; Tripathi, Rudra D; Nautiyal, Chandra S

    2015-07-01

    Trichoderma reesei is an industrially important fungi which also imparts stress tolerance and plant growth promotion in various crops. Arsenic (As) contamination of field soils is one of the challenging problems in agriculture, posing potential threats for both human health and the environment. Plants in association with microbes are a liable method to improve metal tolerance and enhance crop productivity. Chickpea (Cicer arietinum L.), is an important grain legume providing cheap source of protein in semi-arid regions including As affected areas. In this study we report the role of T. reesei NBRI 0716 (NBRI 0716) in supporting chickpea growth and improving soil quality in As simulated conditions. NBRI 0716 modulated the As speciation and its availability to improve grain yield and quality (amino acids and mineral content) in chickpea (C. arietinum L.) plants grown in As spiked soil (100 mg As kg(-1) soil). Arsenic accumulation and speciation results indicate that arsenate [As(V)] was the dominant species in chickpea seeds and rhizosphere soil. The Trichoderma reduced total grain inorganic As (Asi) by 66% and enhanced dimethylarsonic acid (DMA) and monomethylarsinic acid (MMA) content of seed and rhizosphere soil. The results indicate a probable role of NBRI 0716 in As methylation as the possible mechanism for maneuvering As stress in chickpea. Analysis of functional diversity using carbon source utilization (Biolog) showed significant difference in diversity and evenness indices among the soil microbial rhizosphere communities. Microbial diversity loss caused by As were prevented in the presence of Trichoderma NBRI 0716. Copyright © 2015. Published by Elsevier Inc.

  16. Understanding the link between meteorology and speciated abundance of bioaerosols in an urban environment using colocated flow cytometry and real-time autofluorescence measurements

    Science.gov (United States)

    Negron Marty, Arnaldo; DeLeon-Rodriguez, Natasha; Waters, Samantha; Ziemba, Luke; Anderson, Bruce; Bergin, Michael; Konstantinidis, Kostas; Nenes, Athanasios

    2017-04-01

    The abundance and speciation of primary biological atmospheric particles (PBAP) has been of great interest due to their potential impact on human health, cloud formation and contribution to atmospheric nutrient deposition [1, 2]. During this study state-of-the-art sampling techniques and protocols have been developed and combined with the speciation of PBAP by flow cytometry (FCM). An effective FCM protocol has been developed to identify and quantify speciated bioaerosols populations. In addition, a Wideband Integrated Bioaerosol Sensor (WIBS) has been used to understand the temporal variability of the PBAP, by measuring the autofluorescence of the atmospheric particles [3]. The techniques developed here have been applied to understand the PBAP variability and abundance in downtown Atlanta under different meteorological conditions. FCM results show the presence of a low nucleic acid (LNA) and a high nucleic acid (HNA) content subpopulation. The contribution of each subpopulation to the total biological atmospheric particles (TBAP) varies depending on the predominant meteorological conditions. Results suggest the HNA subpopulation, named fungal spores, dominates the composition of the TBAP during humid and warm days after rain events. However, during dry episodes the HNA subpopulation is diminished and the LNA subpopulation dominates the composition of the TBAP in downtown Atlanta. WIBS size distribution shifts between dry periods and humid and warm periods agreed well with the LNA and HNA subpopulations behavior. Our finding suggests Atlanta average PBAP concentration is around 1-8 x 104 part. /m3during Spring, where WIBS represents the lower bound and FCM the upper bound of the quantification. Additional experiments performed with different types of pollen, fungi and bacteria were used to better understand the scattering and fluorescence properties of them under different growing phases. References: [1] Morris, C. E., F. Conen, J. Alex Huffman, V. Phillips, U

  17. Biological therapeutics

    National Research Council Canada - National Science Library

    Greenstein, Ben; Brook, Daniel A

    2011-01-01

    This introductory textbook covers all the main categories of biological medicines, including vaccines, hormonal preparations, drugs for rheumatoid arthritis and other connective tissue diseases, drugs...

  18. How common is ecological speciation in plant-feeding insects? A 'Higher' Nematinae perspective

    Directory of Open Access Journals (Sweden)

    Nyman Tommi

    2010-09-01

    Full Text Available Abstract Background Ecological speciation is a process in which a transiently resource-polymorphic species divides into two specialized sister lineages as a result of divergent selection pressures caused by the use of multiple niches or environments. Ecology-based speciation has been studied intensively in plant-feeding insects, in which both sympatric and allopatric shifts onto novel host plants could speed up diversification. However, while numerous examples of species pairs likely to have originated by resource shifts have been found, the overall importance of ecological speciation in relation to other, non-ecological speciation modes remains unknown. Here, we apply phylogenetic information on sawflies belonging to the 'Higher' Nematinae (Hymenoptera: Tenthredinidae to infer the frequency of niche shifts in relation to speciation events. Results Phylogenetic trees reconstructed on the basis of DNA sequence data show that the diversification of higher nematines has involved frequent shifts in larval feeding habits and in the use of plant taxa. However, the inferred number of resource shifts is considerably lower than the number of past speciation events, indicating that the majority of divergences have occurred by non-ecological allopatric speciation; based on a time-corrected analysis of sister species, we estimate that a maximum of c. 20% of lineage splits have been triggered by a change in resource use. In addition, we find that postspeciational changes in geographic distributions have led to broad sympatry in many species having identical host-plant ranges. Conclusion Our analysis indicates that the importance of niche shifts for the diversification of herbivorous insects is at present implicitly and explicitly overestimated. In the case of the Higher Nematinae, employing a time correction for sister-species comparisons lowered the proportion of apparent ecology-based speciation events from c. 50-60% to around 20%, but such corrections are

  19. Is synthetic biology mechanical biology?

    Science.gov (United States)

    Holm, Sune

    2015-12-01

    A widespread and influential characterization of synthetic biology emphasizes that synthetic biology is the application of engineering principles to living systems. Furthermore, there is a strong tendency to express the engineering approach to organisms in terms of what seems to be an ontological claim: organisms are machines. In the paper I investigate the ontological and heuristic significance of the machine analogy in synthetic biology. I argue that the use of the machine analogy and the aim of producing rationally designed organisms does not necessarily imply a commitment to mechanical biology. The ideal of applying engineering principles to biology is best understood as expressing recognition of the machine-unlikeness of natural organisms and the limits of human cognition. The paper suggests an interpretation of the identification of organisms with machines in synthetic biology according to which it expresses a strategy for representing, understanding, and constructing living systems that are more machine-like than natural organisms.

  20. Environmental impact of toxic elements in red mud studied by fractionation and speciation procedures.

    Science.gov (United States)

    Milačič, Radmila; Zuliani, Tea; Ščančar, Janez

    2012-06-01

    Aluminum (Al) is mostly produced from bauxite ore, which contains up to 70% of Al(2)O(3) (alumina). Before alumina is refined to aluminum metal, it is purified by hot alkaline extraction. As a waste by-product red mud is formed. Due to its high alkalinity and large quantities, it represents a severe disposal problem. In Kidričevo (Slovenia), red mud was washed with water before disposal, and after drying, covered with soil. In Ajka (Hungary), the red mud slurry was collected directly in a containment structure, which burst caused a major accident in October 2010. In the present work the environmental impact of toxic elements in red mud from Kidričevo and Ajka were evaluated by applying a sequential extraction procedure and speciation analysis. The predominant red mud fraction was the insoluble residue; nevertheless, environmental concern was focused on the highly mobile water-soluble fraction of Al and Cr. Al in the water-soluble Ajka mud fraction was present exclusively in form of toxic [Al(OH)(4)](-), while Cr existed in its toxic hexavalent form. Comparative assessment to red mud from Kidričevo (Slovenia) with a lower alkalinity (pH 9) with that from Ajka demonstrated significantly lower Al solubility and the presence of only trace amounts of Cr(VI), confirming that disposal of neutralized mud is environmentally much more acceptable and carries a smaller risk of ecological accidents. Since during the Ajka accident huge amounts of biologically available Al and moderate Cr(VI) concentrations were released into the terrestrial and aquatic environments, monitoring of Al and Cr(VI) set free during remedial actions at the contaminated site is essential. Particular care should be taken to minimize the risk of release of soluble Al species and Cr(VI) into water supplies and surface waters. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Methods for Investigating Mercury Speciation, Transport, Methylation, and Bioaccumulation in Watersheds Affected by Historical Mining

    Science.gov (United States)

    Alpers, C. N.; Marvin-DiPasquale, M. C.; Fleck, J.; Ackerman, J. T.; Eagles-Smith, C.; Stewart, A. R.; Windham-Myers, L.

    2016-12-01

    Many watersheds in the western U.S. have mercury (Hg) contamination from historical mining of Hg and precious metals (gold and silver), which were concentrated using Hg amalgamation (mid 1800's to early 1900's). Today, specialized sampling and analytical protocols for characterizing Hg and methylmercury (MeHg) in water, sediment, and biota generate high-quality data to inform management of land, water, and biological resources. Collection of vertically and horizontally integrated water samples in flowing streams and use of a Teflon churn splitter or cone splitter ensure that samples and subsamples are representative. Both dissolved and particulate components of Hg species in water are quantified because each responds to different hydrobiogeochemical processes. Suspended particles trapped on pre-combusted (Hg-free) glass- or quartz-fiber filters are analyzed for total mercury (THg), MeHg, and reactive divalent mercury. Filtrates are analyzed for THg and MeHg to approximate the dissolved fraction. The sum of concentrations in particulate and filtrate fractions represents whole water, equivalent to an unfiltered sample. This approach improves upon analysis of filtered and unfiltered samples and computation of particulate concentration by difference; volume filtered is adjusted based on suspended-sediment concentration to minimize particulate non-detects. Information from bed-sediment sampling is enhanced by sieving into multiple size fractions and determining detailed grain-size distribution. Wet sieving ensures particle disaggregation; sieve water is retained and fines are recovered by centrifugation. Speciation analysis by sequential extraction and examination of heavy mineral concentrates by scanning electron microscopy provide additional information regarding Hg mineralogy and geochemistry. Biomagnification of MeHg in food webs is tracked using phytoplankton, zooplankton, aquatic and emergent vegetation, invertebrates, fish, and birds. Analysis of zooplankton in

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

    Science.gov (United States)

    Anastasio, C.; Zhang, Q.

    2003-12-01

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

  3. The Composite Regulatory Basis of the Large X-Effect in Mouse Speciation.

    Science.gov (United States)

    Larson, Erica L; Keeble, Sara; Vanderpool, Dan; Dean, Matthew D; Good, Jeffrey M

    2017-02-01

    The disruption of meiotic sex chromosome inactivation (MSCI) has been proposed to be a major developmental mechanism underlying the rapid evolution of hybrid male sterility. We tested this idea by analyzing cell-specific gene expression across spermatogenesis in two lineages of house mice and their sterile and fertile reciprocal hybrids. We found pervasive disruption of sex chromosome gene expression in sterile hybrids at every stage of spermatogenesis. Failure of MSCI was developmentally preceded by increased silencing of autosomal genes, supporting the hypothesis that divergence at the hybrid incompatibility gene, Prdm9, results in increased rates of autosomal asynapsis which in turn triggers widespread silencing of unsynapsed chromatin. We also detected opposite patterns of postmeiotic overexpression or hyper-repression of the sex chromosomes in reciprocal hybrids, supporting the hypothesis that genomic conflict has driven functional divergence that leads to deleterious X-Y dosage imbalances in hybrids. Our developmental timeline also exposed more subtle patterns of mitotic misregulation on the X chromosome, a previously undocumented stage of spermatogenic disruption in this cross. These results indicate that multiple hybrid incompatibilities have converged on a common regulatory phenotype, the disrupted expression of the sex chromosomes during spermatogenesis. Collectively, these data reveal a composite regulatory basis to hybrid male sterility in mice that helps resolve the mechanistic underpinnings of the well-documented large X-effect in mice speciation. We propose that the inherent sensitivity of spermatogenesis to X-linked regulatory disruption has the potential to be a major driver of reproductive isolation in species with chromosomal sex determination. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  4. Arsenic speciation in xylem sap of cucumber (Cucumis sativus L.)

    Energy Technology Data Exchange (ETDEWEB)

    Mihucz, Victor G. [Joint Research Group of Environmental Chemistry of the Hungarian Academy of Sciences and L. Eoetvoes University, Budapest (Hungary); Hungarian Satellite Centre of Trace Elements Institute to UNESCO, Budapest (Hungary); Tatar, Eniko [Hungarian Satellite Centre of Trace Elements Institute to UNESCO, Budapest (Hungary); L. Eoetvoes University, Department of Inorganic and Analytical Chemistry, Budapest (Hungary); Virag, Istvan [L. Eoetvoes University, Department of Inorganic and Analytical Chemistry, Budapest (Hungary); Cseh, Edit; Fodor, Ferenc [L. Eoetvoes University, Department of Plant Physiology, Budapest (Hungary); Zaray, Gyula [Joint Research Group of Environmental Chemistry of the Hungarian Academy of Sciences and L. Eoetvoes University, Budapest (Hungary); Hungarian Satellite Centre of Trace Elements Institute to UNESCO, Budapest (Hungary); L. Eoetvoes University, Department of Inorganic and Analytical Chemistry, Budapest (Hungary)

    2005-10-01

    Flow injection analysis (FIA) and high-performance liquid chromatography double-focusing sector field inductively coupled plasma mass spectrometry (HPLC-DF-ICP-MS) were used for total arsenic determination and arsenic speciation of xylem sap of cucumber plants (Cucumis sativus L.) grown in hydroponics containing 2 {mu}mol dm{sup -3} arsenate or arsenite, respectively. Arsenite [As(III)], arsenate [As(V)] and dimethylarsinic acid (DMA) were identified in the sap of the plants. Arsenite was the predominant arsenic species in the xylem saps regardless of the type of arsenic treatment, and the following concentration order was determined: As(III) > As(V) > DMA. The amount of total As, calculated taking into consideration the mass of xylem sap collected, was almost equal for both treatments. Arsenite was taken up more easily by cucumber than arsenate. Partial oxidation of arsenite to arsenate (<10% in 48 h) was observed in the case of arsenite-containing nutrient solutions, which may explain the detection of arsenate in the saps of plants treated with arsenite. (orig.)

  5. Analysis and speciation of the tritium in environmental matrices

    International Nuclear Information System (INIS)

    Bacchetta, Audrey

    2014-01-01

    This study deals with environmental monitoring. The main aims are (i) the optimisation of the analytical procedure for the tritium in organic form determination, and (ii) the identification of the tritium bearing molecules which are responsible for its transfer from the environment to man. The study was divided into three stages. First an analytical method was developed to determine hydrogen content of several samples, which is a key element to calculate accurate organically bound tritium activities. Secondly, the impact of the organically bound tritium fractions separation (labile exchange) for the determination of the representative fraction of the level of environmental tritium activity was then evaluated. For that, the amount of solubilised sample was estimated. Finally, the speciation of tritium in environmental samples was investigated. Several molecules classes and organic compounds dissolved in the labile exchanges solvent were identified. The results show that the distribution of tritium in organisms depends on both properties of the chemical bond in which it is involved and chemical properties of tritium bearing molecules. The identified compounds belong to the molecules classes such as carbohydrates or amino acids, constitutive of living organisms. It would now be of interest to study the tritium distribution in an environmental sample to target molecules of interest and study the impact of tritium from the environment to man. (author) [fr

  6. Heavy metals speciation in soils treated with sewage sludges

    International Nuclear Information System (INIS)

    Forero Hernandez, Adriana; Ballesteros Gonzalez, Maria Ines

    2004-01-01

    The chemical speciation in soils that had been treated with sewage sludge was determined to find out what had occurred to the heavy metals present. This was done nine weeks after sludge application. An incubation assay was realized using 2.5 % w/w sludge level; this is equivalent to 81.5 ton of sludge per hectare. Pots filled with sludge-soil mixture were placed in a greenhouse at temperature between 17 and 25 Celsius degrade, humidity at field capacity distributed in accordance with a random experimental design with four replicates and seven treatments. It was found that the concentration of Cd, Cu, Mn, Pb, and Zn was lower than the limits established by the environmental protection agency (EPA) for soil usage. Also, the organic carbon content, the available nitrogen and phosphorus were in the normal concentration range reported for organic fertilizers. The sludge addition to the soil gave significant increase of the fraction of Cd bounded to organic material as compared with the exchangeable fraction and the fraction bounded to iron-manganese oxides. Cooper showed more affinity for the fraction of iron-manganese oxides. Lead gave a fraction bounded to organic material that was absent in the witness samples. Zinc had a bigger proportion in the fraction associated with iron manganese oxides. Manganese as compared with the other metals showed the biggest unchangeable fraction

  7. Speciation of cadmium mixed ligand complexes in salt water lakes

    Directory of Open Access Journals (Sweden)

    John L. Kituyi

    2003-06-01

    Full Text Available Amalgam voltammetry has been used to study heavy metal interaction in model lake water in KNO3 at 23 oC at concentration levels of genuine lake water. The hanging drop amalgam electrode was prepared in situ before exchanging the medium for the sample solution. Half-wave potentials at two metal ion concentrations were measured, one at the actual concentration in the lake while the other at a much lower one. The experimentally determined shifts in half-wave potentials are used to compute several formation constants. At the natural [CO32-] of 0.5 M in the lake, the main contributor to the speciation of cadmium is [Cd(CO3Cl2]2-. At high [Cd2+], the DPASV detects the presence of free Cd2+ ions, hence, potential polluting effect, while the amalgam reports [Cd(CO32Cl] 3- to be dominant above [CO32-] = 0.8 M. There is a variation in the number of complexes detected, their stabilities and percentage distribution in the two methods. Cd2+ ion concentration also affects the number of complexes formed and their stabilities.

  8. Speciation of cadmium in seawater - a direct voltammetric approach

    International Nuclear Information System (INIS)

    Helmers, E.

    1994-01-01

    The present report deals with differential pulse anodic stripping voltammetry (DPASV) applied for the analysis of cadmium in open ocean seawater. Evaluation of different Cd species can generate information about distribution and speciation of Cd in the open ocean. Distribution of Cd was investigated in surface waters of the Atlantic Ocean over a wide geographical range as well as in the water column. Surface water sampling on board the research vessel Polarstern was performed from the bow boom of the ship as well as with a snorkel system which allowed continuous sample-taking. Two different Cd species could be differentiated in the voltammograms. UV-irradiation experiments allowed the identification of an inorganic and organic Cd form, the latter caused by the association between Cd and organic matter as e.g. humic substances (HS). Atlantic ocean surface seawater normally contains between 2 and 4 ng organically complexed Cd/kg and no detectable inorganic Cd. Some areas however showed readings of up to 14 ng inorganic Cd/kg in addition. Water column samples exhibited an enrichment of inorganic Cd by depth. Occurrence of inorganic Cd at the surface could be related to specific oceanographical conditions. Together with analytical results of trace metal contents in the particulate phases of surface seawater, new aspects could be established about the biogeochemical cycling of Cd in the sea. (orig.)

  9. Elemental speciation of neptunium in ultra trace amount ranges

    International Nuclear Information System (INIS)

    Stoebener, Nils

    2013-01-01

    In the presented work, the detection of the isotope Np-237 with resonance ionization mass spectrometry (RIMS) was developed and optimized. In RIMS, sample atoms are excited and ionized with laser radiation in several, resonant steps and are subsequently detected by a mass spectrometer. Energy levels suitable for the excitation and ionization of Np-237 were identified using resonance ionization spectroscopy (RIS). With RIS, more than 300 previously unknown electronic states and autoionizing resonances of Np-237 were identified. Using in-source-RIMS, a limit of detection of 9E+5 atoms was demonstrated for the isotope. The mobility of Np in the environment strongly depends on its elemental speciation. Therefore, safety assessments of proposed nuclear waste repositories require analytical methods for the detection of Np species. CE (capillary electrophoresis) was hyphenated to ICP-MS (inductively coupled plasma mass spectrometry) to examine the distribution of the Np redox species Np(IV) and Np(V), which was possible at Np concentrations as low as 1E-9 mol/L. The method was used to study the interaction of the element with Opalinus Clay at varying conditions. CE-ICP-MS revealed, that under the presence of Fe(II), Np(V) is reduced to Np(IV), which is sorbed onto the clay. This leads to a higher overall Np sorption.

  10. Speciation in rapidly diverging systems: lessons from Lake Malawi.

    Science.gov (United States)

    Danley, P D; Kocher, T D

    2001-05-01

    Rapid evolutionary radiations provide insight into the fundamental processes involved in species formation. Here we examine the diversification of one such group, the cichlid fishes of Lake Malawi, which have radiated from a single ancestor into more than 400 species over the past 700 000 years. The phylogenetic history of this group suggests: (i) that their divergence has proceeded in three major bursts of cladogenesis; and (ii) that different selective forces have dominated each cladogenic event. The first episode resulted in the divergence of two major lineages, the sand- and rock-dwellers, each adapted to a major benthic macrohabitat. Among the rock-dwellers, competition for trophic resources then drove a second burst of cladogenesis, which resulted in the differentiation of trophic morphology. The third episode of cladogenesis is associated with differentiation of male nuptial colouration, most likely in response to divergent sexual selection. We discuss models of speciation in relation to this observed pattern. We advocate a model, divergence with gene flow, which reconciles the disparate selective forces responsible for the diversification of this group and suggest that the nonadaptive nature of the tertiary episode has significantly contributed to the extraordinary species richness of this group.

  11. Speciated atmospheric mercury and its potential source in Guiyang, China

    Science.gov (United States)

    Fu, Xuewu; Feng, Xinbin; Qiu, Guangle; Shang, Lihai; Zhang, Hui

    2011-08-01

    Speciated atmospheric mercury (Hg) including gaseous elemental mercury (GEM), particulate Hg (PHg), and reactive gaseous Hg (RGM) were continuously measured at an urban site in Guiyang city, southwest China from August to December 2009. The averaged concentrations for GEM, PHg, and RGM were 9.72 ± 10.2 ng m -3, 368 ± 676 pg m -3, and 35.7 ± 43.9 pg m -3, respectively, which were all highly elevated compared to observations at urban sites in Europe and North America. GEM and PHg were characterized by similar monthly and diurnal patterns, with elevated levels in cold months and nighttime, respectively. In contrast, RGM did not exhibit clear monthly and diurnal variations. The variations of GEM, PHg, and RGM indicate the sampling site was significantly impacted by sources in the city municipal area. Sources identification implied that both residential coal burning and large point sources were responsible to the elevated GEM and PHg concentrations; whereas point sources were the major contributors to elevated RGM concentrations. Point sources played a different role in regulating GEM, PHg, and RGM concentrations. Aside from residential emissions, PHg levels was mostly affected by small-scale coal combustion boilers situated to the east of the sampling site, which were scarcely equipped or lacking particulate control devices; whereas point sources situated to the east, southeast, and southwest of the sampling played an important role on the distribution of atmospheric GEM and RGM.

  12. Characteristics of mercury speciation in Minnesota rivers and streams

    Energy Technology Data Exchange (ETDEWEB)

    Balogh, Steven J. [Metropolitan Council Environmental Services, 2400 Childs Road, St. Paul, MN 55106-6724 (United States)], E-mail: steve.balogh@metc.state.mn.us; Swain, Edward B. [Minnesota Pollution Control Agency, 520 Lafayette Road, St. Paul, MN 55155-4194 (United States)], E-mail: edward.swain@state.mn.us; Nollet, Yabing H. [Metropolitan Council Environmental Services, 2400 Childs Road, St. Paul, MN 55106-6724 (United States)], E-mail: yabing.nollet@metc.state.mn.us

    2008-07-15

    Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs. - Methylmercury and inorganic mercury concentrations in four Minnesota streams were characterized to determine controlling variables.

  13. Speciation of Raney Copper Oxide during High-Temperature Desulfurization

    International Nuclear Information System (INIS)

    Wang, T. C.; Chen, C. Y.; Huang, H.-L.; Wang, H. Paul; Wei Yuling

    2007-01-01

    Speciation of copper in the Raney copper oxides (R-CuO) during high-temperature desulfurization has been studied by X-ray absorption spectroscopy. The preedge XANES spectra (8975-8979 eV) of R-CuO exhibit a very weak 1s-to-3d transition forbidden by the selection rule in the case of the perfect octahedral symmetry. A shoulder at 8985-8988 eV and an intense band at 8994-9002 eV can be attributed to the 1s-to-4p transition that indicates the existence of the Cu(II) species. The preedge band at 8981-8984 eV can be attributed to the dipole-allowed 1s-to-4p transition of Cu(I), suggesting an existence of Cu2S during sulfurization. An enhanced absorbance at 9003 eV shows that Cu(0) species may be formed in the sulfurized R-CuO. The main copper species in regenerated R-CuO are CuO (96%) and Cu2S (4%)

  14. Absorption spectra and speciation of plutonium(VI) with phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Weger, H.T.; Reed, D.

    1996-02-01

    Plutonium(VI)-phosphate species in aqueous solution, at pH < 2.4, formed two species: PuO{sub 2}H{sub 2}PO{sub 4}{sup +} (characterized by an 835 nm absorption band) and the solid phase PuO{sub 2}(H{sub 2}PO{sub 4}){sub 2}. The stability constant {beta} for the PuO{sub 2}H{sub 2}PO{sub 4}{sup +} species was determined to be log {beta} = 2.1 {+-} 0.1 (ionic strength = 0.6--0.9 M) and log {beta}{sup T} = 2.6 {+-} 0.15 (zero ionic strength). Four Pu(VI)-phosphate species (absorption bands at 842, 846, 857, and 866 nm) formed at pH = 2.4 to 12.2 and are characterized by polynuclear behavior, the formation of precipitates, and colloidal properties. The 842 and 846 nm species are believed to be [PuO{sub 2}(HPO{sub 4}){sub m}]{sub n} and [PuO{sub 2}(NaPO{sub 4}){sub m}]{sub n}. The 857 and 866 nm species area as yet unidentified. The speciation of plutonium with phosphate is of interest to radionuclide migration studies because phosphate is present in many groundwaters and may be used as an actinide getter in nuclear waste disposal. An actinide getter is a complexing agent that forms insoluble phases with actinides, thereby reducing their migration.

  15. Speciation of uranium after microbial action by XANES and XPS

    International Nuclear Information System (INIS)

    Dodge, C.J.; Francis, A.J.; Lu, F.; Halada, G.P.; Kagwade, S.V.; Clayton, C.R.

    1993-01-01

    The speciation of radionuclides and toxic metals in wastes subjected to microbial action is important in determining the extent of stabilization in a disposal environment. As part of an ongoing study, we investigated the reduction of uranium by a Clostridium sp. using X-ray absorption neat edge spectroscopy (XANES) at the National Synchrotron Light Source (NSLS) and X-ray photoelectron spectroscopy (XPS). XPS analysis of uranyl acetate containing hexavalent uranium exhibited a binding energy of 382.0eV at the U 4f 7/2 peak. The sample incubated in the presence of bacteria was shifted to lower binding energy (380.6eV), confirming the reduction of U 6+ to U 4+ at the bacterial surface. XANES analysis, using an electron yield detector, was performed at the M v absorption edge (3d-->5f). The absorption peak energy of the sample exhibited a shift from 3551.1eV to 3550.1eV which is higher than uranium metal (3549.6eV ) but lower than U 4+ (3550.4eV). This indicates the presence of U 3+ which is probably located beneath the surface within the biomass. Anaerobic bacterial treatment of wastes containing uranyl ion can result in the stabilization of uranium

  16. Sex chromosome repeats tip the balance towards speciation.

    Science.gov (United States)

    O'Neill, Michael J; O'Neill, Rachel J

    2018-04-06

    Because sex chromosomes, by definition, carry genes that determine sex, mutations that alter their structural and functional stability can have immediate consequences for the individual by reducing fertility, but also for a species by altering the sex ratio. Moreover, the sex-specific segregation patterns of heteromorphic sex chromosomes make them havens for selfish genetic elements that not only create sub-optimal sex ratios, but can also foster sexual antagonism. Compensatory mutations to mitigate antagonism or return sex ratios to a Fisherian optimum can create hybrid incompatibility and establish reproductive barriers leading to species divergence. The destabilizing influence of these selfish elements is often manifest within populations as copy number variants (CNVs) in satellite repeats and transposable elements (TE) or as CNVs involving sex determining genes, or genes essential to fertility and sex chromosome dosage compensation. This review catalogs several examples of well-studied sex chromosome CNVs in Drosophilids and mammals that underlie instances of meiotic drive, hybrid incompatibility and disruptions to sex differentiation and sex chromosome dosage compensation. While it is difficult to pinpoint a direct cause/effect relationship between these sex chromosome CNVs and speciation, it is easy to see how their effects in creating imbalances between the sexes, and the compensatory mutations to restore balance, can lead to lineage splitting and species formation. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  17. Characteristics of mercury speciation in Minnesota rivers and streams

    International Nuclear Information System (INIS)

    Balogh, Steven J.; Swain, Edward B.; Nollet, Yabing H.

    2008-01-01

    Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs. - Methylmercury and inorganic mercury concentrations in four Minnesota streams were characterized to determine controlling variables

  18. Arsenic uptake and speciation in vegetables grown under greenhouse conditions.

    Science.gov (United States)

    Smith, E; Juhasz, A L; Weber, J

    2009-04-01

    The accumulation of arsenic (As) by vegetables is a potential human exposure pathway. The speciation of As in vegetables is an important consideration due to the varying toxicity of different As species. In this study, common Australian garden vegetables were hydroponically grown with As-contaminated irrigation water to determine the uptake and species of As present in vegetable tissue. The highest concentrations of total As were observed in the roots of all vegetables and declined in the aerial portions of the plants. Total As accumulation in the edible portions of the vegetables decreased in the order radish > mung bean > lettuce = chard. Arsenic was present in the roots of radish, chard, and lettuce as arsenate (As(V)) and comprised between 77 and 92% of the total As present, whereas in mung beans, arsenite (As(III)) comprised 90% of the total As present. In aerial portions of the vegetables, As was distributed equally between both As(V) and As(III) in radish and chard but was present mainly as As(V) in lettuce. The presence of elevated As in vegetable roots suggests that As species may be complexed by phytochelatins, which limits As translocation to aerial portions of the plant.

  19. Speciation of platinum(IV) in nitric acid solutions.

    Science.gov (United States)

    Vasilchenko, Danila; Tkachev, Sergey; Baidina, Iraida; Korenev, Sergey

    2013-09-16

    The speciation of platinum(IV) ions in nitric acid (6-15.8 M) solutions of H2[Pt(OH)6] has been studied by (195)Pt NMR and Raman spectroscopy. Series of aqua-hydroxo-nitrato complexes [Pt(L)(x)(NO3)(6-x)] (L = H2O or OH(-); x = 0, ..., 6) were found to exist in such solutions. The pair additivity model of chemical shifts and statistical theory were used to assign signals in NMR spectra to particular [Pt(L)(x)(NO3)(6-x)] species. Mononuclear hexanitratoplatinates(IV) have been isolated in solid state in substantial yield as pyridinium salt (PyH)2[Pt(NO3)6] and characterized by single-crystal X-ray diffraction. Aging of the platinum nitric acid solutions for more than 5-6 h results in oligomerization of [Pt(L)(x)(NO3)(6-x)] species and the formation of oligonuclear aqua-hydroxo-nitrato complexes with OH(-) and NO3(-) bridging ligands. Oligomeric platinum(IV) complexes with two and four nuclei were unambiguously detected by NMR on (195)Pt -enriched samples. Oligomers with even higher nuclearity were also detected. Dimeric anions [Pt2(μ-OH)2(NO3)8](2-) have been isolated as single crystals of tetramethylammonium salt and characterized by X-ray diffraction.

  20. Lead Speciation and Bioavailability in Apatite-Amended Sediments

    Directory of Open Access Journals (Sweden)

    Kirk G. Scheckel

    2011-01-01

    Full Text Available 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 underwent conversion to hydrocerussite and anglesite. Sediments mixed with apatite exhibited limited conversion to pyromorphite, the hypothesized end product. Conversion of PbS to pyromorphite is inhibited under reducing conditions, and pyromorphite formation appears limited to reaction with pore water Pb and PbS oxidation products. Porewater Pb values were decreased by 94% or more when sediment was amended with apatite. The acute toxicity of the sediment Pb was evaluated with Hyalella azteca and bioaccumulation of Pb with Lumbriculus variegatus. The growth of H. azteca may be mildly inhibited in contaminated sediment, with apatite-amended sediments exhibiting on average a higher growth weight by approximately 20%. The bioaccumulation of Pb in L. variegatus tissue decreased with increased phosphate loading in contaminated sediment. The study indicates limited effectiveness of apatite in sequestering Pb if present as PbS under reducing conditions, but sequestration of porewater Pb and stabilization of near-surface sediment may be a feasible and alternative approach to decreasing potential toxicity of Pb.

  1. Toxic heavy metal contamination assessment and speciation in sugarcane soil

    Science.gov (United States)

    Wang, Xiaofei; Deng, Chaobing; Yin, Juan; Tang, Xiang

    2018-01-01

    The increasing heavy metal pollution in the sugarcane soils along the Great Huanjiang River was caused by leakage and spills of Lead (Pb) and Zinc (Zn) tailing dams during a flood event. Copper (Cu), Zn, Pb, Cadmium (Cd), and Arsenic (As) concentrations of soil samples collected from 16 different sites along the Great Huanjiang River coast typical pollution area were analyzed by Inductive Coupled Plasma Mass Spectrometry (ICP-MS). The mean concentrations of Pb, Cd, Zn, Cu, and As in the sugarcane soils were 151.57 mg/kg, 0.33 mg/kg, 155.52 mg/kg, 14.19 mg/kg, and 18.74 mg/kg, respectively. Results from the analysis of heavy metal speciation distribution showed that Cu, Zn, Pb, and Cd existed in weak acid, reducible, and oxidizable fractions, and the sum of these fractions accounted for significant proportions in sugarcane soils. However, the residual fraction of As with high proportion of reducible fraction indicated that this trace element still poses some environmental risk in the sugarcane soils because of its high content. Assessments of pollution levels revealed that the highest environmental risk was arouse by Pb. In addition, moderate to strong Cd and Zn pollution were found, while As has zero to medium level of pollution and Cu has zero level.

  2. Transport methods as complementary tools for speciation purposes

    International Nuclear Information System (INIS)

    Fourest, B.; Sladkov, V.

    2005-01-01

    Transport methods, and especially capillary electrophoresis, are shown to bring with a high simplicity and efficiently useful complementary data to solve some speciation problems. Their application in this aim is particularly interesting in the case of actinides or solutions resulting from the radioactive waste management. In the present article, three examples are proposed to illustrate this point. In the first one, the open-end capillary method is applied to point out the hydrolyzed species of Pa(V) over a wide pH range. The difficulties overcome in this case are related to the very low concentration and specific properties of the element under consideration. The second illustration concerns the complexation of uranyl by the anionic forms of some long-lived fission products (MO x n- , with M=I and Se). For the study of these systems, capillary electrophoresis appears to be a method particularly simple and efficient. The last example deals with the quantification of selenate and selenite ions in the presence of nitrate. Capillary electrophoresis is found to be especially appropriate to the simultaneous determination of these two anionic species in such media. (orig.)

  3. Actinide speciation in the shallow aquifer of Mortandad Canyon

    International Nuclear Information System (INIS)

    Nelson, D.M.; Polzer, W.L.

    1983-01-01

    Treated waste effluent at Los Alamos has been released to the environment in Mortandad Canyon since 1963. A study has been initiated to investigate the relative mobilities of the actinides in the shallow aquifer of Mortandad Canyon. Speciation of radionuclides and their adsorption by sediment are important parameters in the evaluation of those mobilities. Plutonium concentrations and oxidation states were measured in water collected from four test wells (MCO 4, 5, 6, 7.5). A regular decrease in 239 240 Pu concentration was observed with increasing distance from the discharge point. The large difference between the concentrations discharged (30 to 1000 pCi/l for period 1977-1982) and those in the wells (0.02 to 5.4 pCi/l) suggests that progressive loss of plutonium from the water as it moves through the alluvium is probably more important in regulating the concentrations than the variability of concentrations in the discharged effluent. The K/sub D/s for 228 Th were also determined and found to be similar to those for plutonium. The factors regulating the concentration of dissolved plutonium are probably the same as those regulating 228 Th. In contrast the K/sub D/s of 241 Am decrease regularly with distance from the discharge point and are about 100 times lower than those of plutonium and thorium for water in wells farthest from the discharge point

  4. Speciation and reduced hybrid female fertility in house mice.

    Science.gov (United States)

    Suzuki, Taichi A; Nachman, Michael W

    2015-09-01

    In mammals, intrinsic postzygotic isolation has been well studied in males but has been less studied in females, despite the fact that female gametogenesis and pregnancy provide arenas for hybrid sterility or inviability that are absent in males. Here, we asked whether inviability or sterility is observed in female hybrids of Mus musculus domesticus and M. m. musculus, taxa which hybridize in nature and for which male sterility has been well characterized. We looked for parent-of-origin growth phenotypes by measuring adult body weights in F1 hybrids. We evaluated hybrid female fertility by crossing F1 females to a tester male and comparing multiple reproductive parameters between intrasubspecific controls and intersubspecific hybrids. Hybrid females showed no evidence of parent-of-origin overgrowth or undergrowth, providing no evidence for reduced viability. However, hybrid females had smaller litter sizes, reduced embryo survival, fewer ovulations, and fewer small follicles relative to controls. Significant variation in reproductive parameters was seen among different hybrid genotypes, suggesting that hybrid incompatibilities are polymorphic within subspecies. Differences in reproductive phenotypes in reciprocal genotypes were observed and are consistent with cyto-nuclear incompatibilities or incompatibilities involving genomic imprinting. These findings highlight the potential importance of reduced hybrid female fertility in the early stages of speciation. © 2015 The Author(s). Evolution © 2015 The Society for the Study of Evolution.

  5. NEARSOL, Aqueous Speciation and Solubility of Actinides for Waste Disposal

    International Nuclear Information System (INIS)

    Leach, S.J.; Pryke, D.C.

    1989-01-01

    A - Description of program or function: NEARSOL models the aqueous speciation and solubility of actinides under near-field conditions for disposal using a simple thermodynamic approach. B - Method of solution: The program draws information from a thermodynamic data base consisting of solubility products and complex formation constants for all known species, and standard electrode potentials, at 25 C, corrected for ionic strength effects. By minimising the free energy of the system through a series of iterations, a precipitating solid phase is predicted which limits the solubility, and the concentration of the main aqueous species are calculated as a function of pH. Initially the program evaluates only hydroxide and carbonate species, but the effect of sulphate, phosphate and fluoride anions can also be included. The program is simple to use, requiring inputs of: 1. Actinide(s); 2. pH range; 3. Ionic strength; 4. Redox conditions; 5. Ligand concentrations. Functions are included to calculate the distribution of the protonated and un-protonated forms of carbonate and phosphate and the value of Eh as a function of pH under disposal conditions as required. The program can further evaluate the role of free calcium ions. C - Restrictions on the complexity of the problem: None

  6. Computational biology

    DEFF Research Database (Denmark)

    Hartmann, Lars Røeboe; Jones, Neil; Simonsen, Jakob Grue

    2011-01-01

    Computation via biological devices has been the subject of close scrutiny since von Neumann’s early work some 60 years ago. In spite of the many relevant works in this field, the notion of programming biological devices seems to be, at best, ill-defined. While many devices are claimed or proved t...

  7. Mesoscopic biology

    Indian Academy of Sciences (India)

    In this paper we present a qualitative outlook of mesoscopic biology where the typical length scale is of the order of nanometers and the energy scales comparable to thermal energy. Novel biomolecular machines, governed by coded information at the level of DNA and proteins, operate at these length scales in biological ...

  8. Male-male competition and speciation : aggression bias towards differently coloured rivals varies between stages of speciation in a Lake Victoria cichlid species complex

    NARCIS (Netherlands)

    Dijkstra, P. D.; Seehausen, O.; Pierotti, M. E. R.; Groothuis, T. G. G.

    Sympatric speciation driven by sexual selection by female mate choice on a male trait is a much debated topic. The process is problematic because of the lack of negative frequency-dependent selection that can facilitate the invasion of a novel colour phenotype and stabilize trait polymorphism. It

  9. Use of ion-pairing reagent for improving iodine speciation analysis in seaweed by pressure-driven capillary electrophoresis and ultraviolet detection.

    Science.gov (United States)

    Sun, Jiannan; Wang, Dan; Cheng, Heyong; Liu, Jinhua; Wang, Yuanchao; Xu, Zigang

    2015-01-30

    This study achieved resolution improvement for iodine speciation in the presence of an ion-pairing reagent by a pressure-driven capillary electrophoresis (CE) system. Addition of 0.01mM tetrabutyl ammonium hydroxide (TBAH) as the ion-pairing reagent into the electrophoretic buffer resulted in the complete separation of four iodine species (I(-), IO3(-), mono-iodothyrosine-MIT and di-iodothyrosine-DIT), because of the electrostatic interaction between TBAH and the negatively charged analytes. A +16kV separation voltage was applied along the separation capillary (50μm i.d., 80cm total and 60cm effective) with the inlet grounded. The detection wavelength was fixed at 210nm, and the pressure-driven flow rate was set at 0.12mLmin(-1) with an injected volume of 2μL. The optimal electrolyte consisted of 2mM borate, 2mM TBAH and 80% methanol with pH adjusted to 8.5. Baseline separation of iodine species was achieved within 7min. The detection limits for I(-), IO3(-), MIT and DIT were 0.052, 0.040, 0.032 and 0.025mgL(-1), respectively. The relative standard deviations of peak heights and areas were all below 3% for 5mgL(-1) and 5% for 1mgL(-1). Application of the proposed method was demonstrated by speciation analysis of iodine in two seaweed samples. The developed method offered satisfactory recoveries in the 91-99% range and good precisions (iodine speciation in environmental, food and biological samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Quantum Biology

    Directory of Open Access Journals (Sweden)

    Alessandro Sergi

    2009-06-01

    Full Text Available A critical assessment of the recent developmentsof molecular biology is presented.The thesis that they do not lead to a conceptualunderstanding of life and biological systems is defended.Maturana and Varela's concept of autopoiesis is briefly sketchedand its logical circularity avoided by postulatingthe existence of underlying living processes,entailing amplification from the microscopic to the macroscopic scale,with increasing complexity in the passage from one scale to the other.Following such a line of thought, the currently accepted model of condensed matter, which is based on electrostatics and short-ranged forces,is criticized. It is suggested that the correct interpretationof quantum dispersion forces (van der Waals, hydrogen bonding, and so onas quantum coherence effects hints at the necessity of includinglong-ranged forces (or mechanisms for them incondensed matter theories of biological processes.Some quantum effects in biology are reviewedand quantum mechanics is acknowledged as conceptually important to biology since withoutit most (if not all of the biological structuresand signalling processes would not even exist. Moreover, it is suggested that long-rangequantum coherent dynamics, including electron polarization,may be invoked to explain signal amplificationprocess in biological systems in general.

  11. Biological desulfurisation

    Energy Technology Data Exchange (ETDEWEB)

    Arena, B.J. [UOP LLC (United States); Benschop, A.; Janssen, A. [Paques Natural Solutions (Netherlands); Kijlstra, S. [Shell Global Solutions (Netherlands)

    2001-03-01

    This article focuses on the biological THIOPAQ process for removing hydrogen sulphide from refinery gases and recovering elemental sulphur. Details are given of the process which absorbs hydrogen sulphide-containing gas in alkaline solution prior to oxidation of the dissolved sulphur to elemental sulphur in a THIOPAQ aerobic biological reactor, with regeneration of the caustic solution. Sulphur handling options including sulphur wash, the drying of the sulphur cake, and sulphur smelting by pressure liquefaction are described. Agricultural applications of the biologically recovered sulphur, and application of the THIOPAQ process to sulphur recovery are discussed.

  12. Pollinator-driven ecological speciation in plants: new evidence and future perspectives.

    Science.gov (United States)

    Van der Niet, Timotheüs; Peakall, Rod; Johnson, Steven D

    2014-01-01

    The hypothesis that pollinators have been important drivers of angiosperm diversity dates back to Darwin, and remains an important research topic today. Mounting evidence indicates that pollinators have the potential to drive diversification at several different stages of the evolutionary process. Microevolutionary studies have provided evidence for pollinator-mediated floral adaptation, while macroevolutionary evidence supports a general pattern of pollinator-driven diversification of angiosperms. However, the overarching issue of whether, and how, shifts in pollination system drive plant speciation represents a critical gap in knowledge. Bridging this gap is crucial to fully understand whether pollinator-driven microevolution accounts for the observed macroevolutionary patterns. Testable predictions about pollinator-driven speciation can be derived from the theory of ecological speciation, according to which adaptation (microevolution) and speciation (macroevolution) are directly linked. This theory is a particularly suitable framework for evaluating evidence for the processes underlying shifts in pollination systems and their potential consequences for the evolution of reproductive isolation and speciation. This Viewpoint paper focuses on evidence for the four components of ecological speciation in the context of plant-pollinator interactions, namely (1) the role of pollinators as selective agents, (2) floral trait divergence, including the evolution of 'pollination ecotypes', (3) the geographical context of selection on floral traits, and (4) the role of pollinators in the evolution of reproductive isolation. This Viewpoint also serves as the introduction to a Special Issue on Pollinator-Driven Speciation in Plants. The 13 papers in this Special Issue range from microevolutionary studies of ecotypes to macroevolutionary studies of historical ecological shifts, and span a wide range of geographical areas and plant families. These studies further illustrate

  13. Pollinator-driven ecological speciation in plants: new evidence and future perspectives

    Science.gov (United States)

    Van der Niet, Timotheüs; Peakall, Rod; Johnson, Steven D.

    2014-01-01

    Background The hypothesis that pollinators have been important drivers of angiosperm diversity dates back to Darwin, and remains an important research topic today. Mounting evidence indicates that pollinators have the potential to drive diversification at several different stages of the evolutionary process. Microevolutionary studies have provided evidence for pollinator-mediated floral adaptation, while macroevolutionary evidence supports a general pattern of pollinator-driven diversification of angiosperms. However, the overarching issue of whether, and how, shifts in pollination system drive plant speciation represents a critical gap in knowledge. Bridging this gap is crucial to fully understand whether pollinator-driven microevolution accounts for the observed macroevolutionary patterns. Testable predictions about pollinator-driven speciation can be derived from the theory of ecological speciation, according to which adaptation (microevolution) and speciation (macroevolution) are directly linked. This theory is a particularly suitable framework for evaluating evidence for the processes underlying shifts in pollination systems and their potential consequences for the evolution of reproductive isolation and speciation. Scope This Viewpoint paper focuses on evidence for the four components of ecological speciation in the context of plant-pollinator interactions, namely (1) the role of pollinators as selective agents, (2) floral trait divergence, including the evolution of ‘pollination ecotypes‘, (3) the geographical context of selection on floral traits, and (4) the role of pollinators in the evolution of reproductive isolation. This Viewpoint also serves as the introduction to a Special Issue on Pollinator-Driven Speciation in Plants. The 13 papers in this Special Issue range from microevolutionary studies of ecotypes to macroevolutionary studies of historical ecological shifts, and span a wide range of geographical areas and plant families. These studies

  14. Hybridization masks speciation in the evolutionary history of the Galápagos marine iguana

    Science.gov (United States)

    MacLeod, Amy; Rodríguez, Ariel; Vences, Miguel; Orozco-terWengel, Pablo; García, Carolina; Trillmich, Fritz; Gentile, Gabriele; Caccone, Adalgisa; Quezada, Galo; Steinfartz, Sebastian

    2015-01-01

    The effects of the direct interaction between hybridization and speciation—two major contrasting evolutionary processes—are poorly understood. We present here the evolutionary history of the Galápagos marine iguana (Amblyrhynchus cristatus) and reveal a case of incipient within-island speciation, which is paralleled by between-island hybridization. In-depth genome-wide analyses suggest that Amblyrhynchus diverged from its sister group, the Galápagos land iguanas, around 4.5 million years ago (Ma), but divergence among extant populations is exceedingly young (less than 50 000 years). Despite Amblyrhynchus appearing as a single long-branch species phylogenetically, we find strong population structure between islands, and one case of incipient speciation of sister lineages within the same island—ostensibly initiated by volcanic events. Hybridization between both lineages is exceedingly rare, yet frequent hybridization with migrants from nearby islands is evident. The contemporary snapshot provided by highly variable markers indicates that speciation events may have occurred throughout the evolutionary history of marine iguanas, though these events are not visible in the deeper phylogenetic trees. We hypothesize that the observed interplay of speciation and hybridization might be a mechanism by which local adaptations, generated by incipient speciation, can be absorbed into a common gene pool, thereby enhancing the evolutionary potential of the species as a whole. PMID:26041359

  15. Speciation on a local geographic scale: the evolution of a rare rock outcrop specialist in Mimulus.

    Science.gov (United States)

    Ferris, Kathleen G; Sexton, Jason P; Willis, John H

    2014-08-05

    Speciation can occur on both large and small geographical scales. In plants, local speciation, where small populations split off from a large-ranged progenitor species, is thought to be the dominant mode, yet there are still few examples to verify speciation has occurred in this manner. A recently described morphological species in the yellow monkey flowers, Mimulus filicifolius, is an excellent candidate for local speciation because of its highly restricted geographical range. Mimulus filicifolius was formerly identified as a population of M. laciniatus due to similar lobed leaf morphology and rocky outcrop habitat. To investigate whether M. filicifolius is genetically divergent and reproductively isolated from M. laciniatus, we examined patterns of genetic diversity in ten nuclear and eight microsatellite loci, and hybrid fertility in M. filicifolius and its purported close relatives: M. laciniatus, M. guttatus and M. nasutus. We found that M. filicifolius is genetically divergent from the other species and strongly reproductively isolated from M. laciniatus. We conclude that M. filicifolius is an independent rock outcrop specialist despite being morphologically and ecologically similar to M. laciniatus, and that its small geographical range nested within other wide-ranging members of the M. guttatus species complex is consistent with local speciation. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

  16. Evidence for nonallopatric speciation among closely related sympatric Heliotropium species in the Atacama Desert.

    Science.gov (United States)

    Luebert, Federico; Jacobs, Pit; Hilger, Hartmut H; Muller, Ludo A H

    2014-02-01

    The genetic structure of populations of closely related, sympatric species may hold the signature of the geographical mode of the speciation process. In fully allopatric speciation, it is expected that genetic differentiation between species is homogeneously distributed across the genome. In nonallopatric speciation, the genomes may remain undifferentiated to a large extent. In this article, we analyzed the genetic structure of five sympatric species from the plant genus Heliotropium in the Atacama Desert. We used amplified fragment length polymorphisms (AFLPs) to characterize the genetic structure of these species and evaluate their genetic differentiation as well as the number of loci subject to positive selection using divergence outlier analysis (DOA). The five species form distinguishable groups in the genetic space, with zones of overlap, indicating that they are possibly not completely isolated. Among-species differentiation accounts for 35% of the total genetic differentiation (F ST = 0.35), and F ST between species pairs is positively correlated with phylogenetic distance. DOA suggests that few loci are subject to positive selection, which is in line with a scenario of nonallopatric speciation. These results support the idea that sympatric species of Heliotropium sect. Cochranea are under an ongoing speciation process, characterized by a fluctuation of population ranges in response to pulses of arid and humid periods during Quaternary times.

  17. Influence of natural organic matter on the speciation of radionuclides in a geochemistry context

    International Nuclear Information System (INIS)

    Marang, L.

    2007-09-01

    The principal aim of this work is the study of the influence of natural organic matter, in particularly humic substances (HS), on the speciation of radionuclides (RN). The studied radionuclides are cobalt (II), europium (III) and uranium (VI). It has been shown that mobility and bioavailability of a metal are related to its speciation. The NICA-Donnan model describes metal ion binding to NOM: it accounts for NOM chemical heterogeneity, competition during binding and ionic strength effects. However the model has been calibrated with a limited number of experimental data for the RN. Indeed there is only a few speciation technique available for the study of the interactions RN-HS. Within the framework of this study, we have developed and optimised speciation technique (Flux Donnan Membrane Technique and the use of an un-solubilized humic acid) in order to acquire new experimental data, we have also studied the effect of the competition on RN speciation and finally we have tested the model capacity to predict the RN behavior in laboratory or in situ. (author)

  18. Influence of natural organic matter on the speciation of radionuclides in a geochemistry context

    International Nuclear Information System (INIS)

    Marang, L.

    2007-09-01

    The principal aim of this work is the study of the influence of natural organic matter, in particularly humic substances (HS), on the speciation of radionuclides (RN). The studied radionuclides are cobalt (II), europium (III) and uranium (VI). It has been shown that mobility and bioavailability of a metal are related to its speciation. The NICA-Donnan model describes metal ion binding to NOM: it accounts for NOM chemical heterogeneity, competition during binding and ionic strength effects. However the model has been calibrated with a limited number of experimental data for the RN. Indeed there is only a few speciation techniques available for the study of the interactions RN-HS. Within the framework of this study, we have developed and optimised speciation technique (Flux Donnan Membrane Technique and the use of an insolubilized humic acid) in order to acquire new experimental data, we have also studied the effect of the competition on RN speciation and finally we have tested the model capacity to predict the RN behavior in laboratory or in situ. (author)

  19. Progress report on SYVAC chemical speciation modelling studies during 1983/4

    International Nuclear Information System (INIS)

    Cross, J.; Smith, G.L.; Williams, D.R.

    1984-01-01

    This report summarises progress made on the SYVAC (System Variability Analysis program) chemical speciation project during 1983-4. Chemical speciation is defined and its importance in the SYVAC approach to Radioactive Waste Management is discussed. Computer modelling of chemical equilibria is described and the two programs presently operational at UWIST - SOLMNQ and MINEQL - are compared and discussed in detail. In view of the shortcomings of the databases supplied with these programs, a new database of equilibrium constants has been compiled containing 483 aqueous species and 329 solid phases, including data for the radionuclides uranium, plutonium, americium, neptunium and thorium. The collaborative work with AERE, Harwell, is reported. A leaching experiment carried out at Harwell has been modelled using the chemical speciation programs. The results for uranium, plutonium, americium and neptunium, are presented. However, the experimental data provided by AERE is insufficient for accurate simulations. Chemical speciation studies relating to specific sites require accurate characterisation of the groundwater, i.e. chemical composition, Eh and pH. In the absence of such information, preliminary studies have been made using an average granite groundwater. The results of these studies are presented and include solubility and speciation plots for uranium, plutonium, thorium and neptunium. The future aims of the project are discussed. (author)

  20. Moran model as a dynamical process on networks and its implications for neutral speciation

    Science.gov (United States)

    de Aguiar, Marcus A. M.; Bar-Yam, Yaneer

    2011-03-01

    In population genetics, the Moran model describes the neutral evolution of a biallelic gene in a population of haploid individuals subjected to mutations. We show in this paper that this model can be mapped into an influence dynamical process on networks subjected to external influences. The panmictic case considered by Moran corresponds to fully connected networks and can be completely solved in terms of hypergeometric functions. Other types of networks correspond to structured populations, for which approximate solutions are also available. This approach to the classic Moran model leads to a relation between regular networks based on spatial grids and the mechanism of isolation by distance. We discuss the consequences of this connection for topopatric speciation and the theory of neutral speciation and biodiversity. We show that the effect of mutations in structured populations, where individuals can mate only with neighbors, is greatly enhanced with respect to the panmictic case. If mating is further constrained by genetic proximity between individuals, a balance of opposing tendencies takes place: increasing diversity promoted by enhanced effective mutations versus decreasing diversity promoted by similarity between mates. Resolution of large enough opposing tendencies occurs through speciation via pattern formation. We derive an explicit expression that indicates when speciation is possible involving the parameters characterizing the population. We also show that the time to speciation is greatly reduced in comparison with the panmictic case.

  1. Speciation of neptunium after diffusion in Opalinus Clay

    Energy Technology Data Exchange (ETDEWEB)

    Reich, Tobias; Amayri, Samer; Drebert, Jakob; Froehlich, Daniel R.; Grolimund, Daniel; Rosemann, Jonathan [Mainz Univ. (Germany). Inst. of Nuclear Chemistry; Kaplan, Ugras [Paul Scherrer Institut, Villigen (Switzerland). Swiss Light Source

    2015-07-01

    Argillaceous rock formations are under consideration as a potential host rock for the construction of high-level nuclear waste repositories. Under environmental conditions the most stable oxidation states of {sup 237}Np (t{sub 1/2}=2.1 x 10{sup 6} a) are Np(IV) and Np(V). We have investigated the sorption and diffusion of the more mobile Np(V) in Opalinus Clay (OPA, Mont Terri, Switzerland) (Wu et al. 2009, Froehlich et al. 2011 and 2012 a). OPA, which is present in Switzerland and southern Germany, possesses a micro-scale heterogeneity and is composed of several types of clay minerals, but also of calcite, quartz and iron(II)-bearing minerals. In our previous diffusion (Wu et al. 2009) and anaerobic sorption experiments (Froehlich et al. 2011), we observed higher distribution coefficients, K{sub d}, than expected from batch experiments performed in air, indicating that a partial reduction of Np(V) to Np(IV) had occurred. To test this hypothesis, different sorption and diffusion samples with Np(V) were prepared at pH 7.6 for spatially resolved molecular-level investigations at the microXAS beamline at the Swiss Light Source (PSI, Villigen, Switzerland) (Froehlich et al. 2012 b). Elemental distributions of Ca, Fe and Np have been determined by μ-XRF mapping. Regions of high Np concentration were subsequently investigated by Np L{sub III}-edge μ-XANES. In most samples Np spots with considerable amounts of tetravalent Np could be found, even when the experiments were performed under ambient-air conditions. In some cases, almost pure Np(IV) L{sub III}-edge XANES spectra were recorded. In case of the anaerobic sorption sample, a clear correlation between Np and Fe was observed by μ-XRF, indicating that iron(II)-bearing minerals could be responsible for the reduction of Np(V). μ-XRD measurements of this sample showed that pyrite is at least one of the redox-active phases determining the speciation of Np in OPA. In this case, Np was accumulated on pyrite, indicating

  2. Systems Biology

    Indian Academy of Sciences (India)

    IAS Admin

    study and understand the function of biological systems, particu- larly, the response of such .... understand the organisation and behaviour of prokaryotic sys- tems. ... relationship of the structure of a target molecule to its ability to bind a certain ...

  3. Systemic distribution and speciation of diphenylarsinic acid fed to rats

    International Nuclear Information System (INIS)

    Naranmandura, Hua; Suzuki, Noriyuki; Takano, Juniti; McKnight-Whitford, Tony; Ogra, Yasumitsu; Suzuki, Kazuo T.; Le, X. Chris

    2009-01-01

    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 2 O 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.

  4. Molecular and supramolecular speciation of monoamide extractant systems

    International Nuclear Information System (INIS)

    Ferru, G.

    2012-01-01

    DEHiBA (N,N-di-(ethyl-2-hexyl)isobutyramide, a monoamide, was chosen as selective extractant for the recovery of uranium in the first cycle of the GANEX process, which aims to realize the grouped extraction of actinides in the second step of the process. The aim of this work is an improved description of monoamide organic solutions in alkane diluent after solutes extraction: water, nitric acid and uranyl nitrate. A parametric study was undertaken to characterize species at molecular scale (by IR spectroscopy, UV-visible spectroscopy, time-resolved laser-induced fluorescence spectroscopy, and electro-spray ionisation mass spectrometry) and at supramolecular scale (by vapor pressure osmometry and small angle X-ray scattering coupled to molecular dynamic simulations). Extraction isotherms were modelled taking into account the molecular and supramolecular speciation. These works showed that the organization of the organic solution depends on the amide concentration, the nature and the concentration of the extracted solute. Three regimes can be distinguished. 1/For extractant concentration less than 0.5 mol/L, monomers are predominate species. 2/ For extractant concentrations between 0.5 and 1 mol/L, small aggregates are formed containing 2 to 4 molecules of monoamide. 3/ For more concentrated solutions (greater than 1 mol/L), slightly larger species can be formed after water or nitric acid extraction. Concerning uranyl nitrate extraction, an important and strong organization of the organic phase is observed, which no longer allows the formation of well spherical defined aggregates. At molecular scale, complexes are not sensitive to the organization of the solution: the same species are observed, regardless of the solute and extractant concentrations in organic phase. (author) [fr

  5. Speciation and transport of radionuclides in ground water

    International Nuclear Information System (INIS)

    Robertson, D.E.; Toste, A.P.; Abel, K.H.; Cowan, C.E.; Jenne, E.A.; Thomas, C.W.

    1984-01-01

    Studies of the chemical speciation of a number of radionuclides migrating in a slightly contaminated ground water plume are identifying the most mobile species and providing an opportunity to test and/or validate geochemical models of radionuclide transport in ground waters. Results to date have shown that most of the migrating radionuclides are present in anionic or nonionic forms. These include anionic forms of 55 Fe, 60 Co, /sup 99m/Tc, 106 Ru, 131 I, and nonionic forms of 63 Ni and 125 Sb. Strontium-70 and a small fraction of the mobile 60 Co are the only cationic radionuclides which have been detected moving in the ground water plume beyond 30 meters from the source. A comparison of the observed chemical forms with the predicted species calculated from modeling thermodynamic data and ground water chemical parameters has indicated a good agreement for most of the radioelements in the system, including Tc, Np, Cs, Sr, Ce, Ru, Sb, Zn, and Mn. The discrepancies between observed and calculated solutions species were noted for Fe, Co, Ni and I. Traces of Fe, Co, and Ni were observed to migrate in anionic or nonionic forms which the calculations failed to predict. These anionic/nonionic species may be organic complexes having enhanced mobility in ground waters. The radioiodine, for example, was shown to behave totally as an anion but further investigation revealed that 49-57% of this anionic iodine was organically bound. The ground water and aqueous extracts of trench sediments contain a wide variety of organic compounds, some of which could serve as complexing agents for the radionuclides. These results indicate the need for further research at a variety of field sites in defining precisely the chemical forms of the mobile radionuclide species, and in better understanding the role of dissolved organic materials in ground water transport of radionuclides

  6. Analytical artefacts in the speciation of arsenic in clinical samples

    International Nuclear Information System (INIS)

    Slejkovec, Zdenka; Falnoga, Ingrid; Goessler, Walter; Elteren, Johannes T. van; Raml, Reingard; Podgornik, Helena; Cernelc, Peter

    2008-01-01

    Urine and blood samples of cancer patients, treated with high doses of arsenic trioxide were analysed for arsenic species using HPLC-HGAFS and, in some cases, HPLC-ICPMS. Total arsenic was determined with either flow injection-HGAFS in urine or radiochemical neutron activation analysis in blood fractions (in serum/plasma, blood cells). The total arsenic concentrations (during prolonged, daily/weekly arsenic trioxide therapy) were in the μg mL -1 range for urine and in the ng g -1 range for blood fractions. The main arsenic species found in urine were As(III), MA and DMA and in blood As(V), MA and DMA. With proper sample preparation and storage of urine (no preservation agents/storage in liquid nitrogen) no analytical artefacts were observed and absence of significant amounts of alleged trivalent metabolites was proven. On the contrary, in blood samples a certain amount of arsenic can get lost in the speciation procedure what was especially noticeable for the blood cells although also plasma/serum gave rise to some disappearance of arsenic. The latter losses may be attributed to precipitation of As(III)-containing proteins/peptides during the methanol/water extraction procedure whereas the former losses were due to loss of specific As(III)-complexing proteins/peptides (e.g. cysteine, metallothionein, reduced GSH, ferritin) on the column (Hamilton PRP-X100) during the separation procedure. Contemporary analytical protocols are not able to completely avoid artefacts due to losses from the sampling to the detection stage so that it is recommended to be careful with the explanation of results, particularly regarding metabolic and pharmacokinetic interpretations, and always aim to compare the sum of species with the total arsenic concentration determined independently

  7. Whole-genome analyses of speciation events in pathogenic Brucellae

    Energy Technology Data Exchange (ETDEWEB)

    Chain, Patrick S. G. [Lawrence Livermore National Laboratory (LLNL); Comerci, Diego J. [Universidad Nacional de General San Martin; Tolmasky, Marcelo E. [California State University; Larimer, Frank W [ORNL; Malfatti, Stephanie [Lawrence Livermore National Laboratory (LLNL); Vergez, Lisa [Lawrence Livermore National Laboratory (LLNL); Aguero, Fernan [Universidad Nacional de General San Martin; Land, Miriam L [ORNL; Ugalde, Rodolfo A. [Universidad Nacional de General San Martin; Garcia, Emilio [Lawrence Livermore National Laboratory (LLNL)

    2005-12-01

    Despite their high DNA identity and a proposal to group classical Brucella species as biovars of Brucella melitensis, the commonly recognized Brucella species can be distinguished by distinct biochemical and fatty acid characters, as well as by a marked host range (e.g., Brucella suis for swine, B. melitensis for sheep and goats, and Brucella abortus for cattle). Here we present the genome of B. abortus 2308, the virulent prototype biovar 1 strain, and its comparison to the two other human pathogenic Brucella species and to B. abortus field isolate 9-941. The global distribution of pseudogenes, deletions, and insertions supports previous indications that B. abortus and B. melitensis share a common ancestor that diverged from B. suis. With the exception of a dozen genes, the genetic complements of both B. abortus strains are identical, whereas the three species differ in gene content and pseudogenes. The pattern of species-specific gene inactivations affecting transcriptional regulators and outer membrane proteins suggests that these inactivations may play an important role in the establishment of host specificity and may have been a primary driver of speciation in the genus Brucella. Despite being nonmotile, the brucellae contain flagellum gene clusters and display species-specific flagellar gene inactivations, which lead to the putative generation of different versions of flagellum-derived structures and may contribute to differences in host specificity and virulence. Metabolic changes such as the lack of complete metabolic pathways for the synthesis of numerous compounds (e.g., glycogen, biotin, NAD, and choline) are consistent with adaptation of brucellae to an intracellular life-style.

  8. Extensive gene flow over Europe and possible speciation

    Energy Technology Data Exchange (ETDEWEB)

    VINCENOT, Dr. LUCIE [Centre d’Ecologie Fonctionnelle et Evolutive Montpellier, France; NARA, Dr. KAZUHIDE [Department of Natural Environmental Studies, The University of Tokyo, Japan; STHULTZ, CHRISTOPHER [Centre d’Ecologie Fonctionnelle et Evolutive Montpellier, France; Labbe, Jessy L [ORNL; DUBOIS, MARIE-PIERRE [Centre d’Ecologie Fonctionnelle et Evolutive Montpellier, France; TEDERSOO, LEHO [University of Tartu, Estonia; Martin, Francis [INRA, Nancy, France; SELOSSE, Dr. MARC-ANDRE [Centre d’Ecologie Fonctionnelle et Evolutive Montpellier, France

    2012-01-01

    Biogeographical patterns and large-scale genetic structure have been little studied in ectomycorrhizal (EM) fungi, despite the ecological and economic importance of EM symbioses. We coupled population genetics and phylogenetic approaches to understand spatial structure in fungal populations on a continental scale. Using nine microsatellite markers, we characterized gene flow among 16 populations of the widespread EM basidiomycete Laccaria amethystina over Europe (i.e. over 2900 km). We also widened our scope to two additional populations from Japan (104 km away) and compared them with European populations through microsatellite markers and multilocus phylogenies, using three nuclear genes (NAR, G6PD and ribosomal DNA) and two mitochondrial ribosomal genes. European L. amethystina populations displayed limited differentiation (average FST = 0.041) and very weak isolation by distance (IBD). This panmictic European pattern may result from effective aerial dispersal of spores, high genetic diversity in populations and mutualistic interactions with multiple hosts that all facilitate migration. The multilocus phylogeny based on nuclear genes confirmed that Japanese and European specimens were closely related but clustered on a geographical basis. By using microsatellite markers, we found that Japanese populations were strongly differentiated from the European populations (FST = 0.416), more than expected by extrapolating the European pattern of IBD. Population structure analyses clearly separated the populations into two clusters, i.e. European and Japanese clusters. We discuss the possibility of IBD in a continuous population (considering some evidence for a ring species over the Northern Hemisphere) vs. an allopatric speciation over Eurasia, making L. amethystina a promising model of intercontinental species for future studies.

  9. Speciation and isotopic exchangeability of nickel in soil solution.

    Science.gov (United States)

    Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

    2009-01-01

    Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. In this study, free Ni(2+) activities were determined in pore waters of long-term Ni-contaminated soils using a Donnan dialysis membrane technique. The pore water free Ni(2+) concentration as a percentage of total soluble Ni ranged from 21 to 80% (average 53%), and the average amount of Ni bound to dissolved organic matter estimated by Windermere Humic Aqueous Model VI was < or = 17%. These data indicate that complexed forms of Ni can constitute a significant fraction of total Ni in solution. Windermere Humic Aqueous Model VI provided reasonable estimates of free Ni(2+) fractions in comparison to the measured fractions (R(2) = 0.83 with a slope of 1.0). Also, the isotopically exchangeable pools (E value) of soil Ni were measured by an isotope dilution technique using water extraction, with and without resin purification, and 0.1 mol L(-1) CaCl(2) extraction, and the isotopic exchangeability of Ni species in soil water extracts was investigated. The concentrations of isotopically non-exchangeable Ni in water extracts were <9% of total water soluble Ni concentrations for all soils. The resin E values expressed as a percentage of the total Ni concentrations in soil showed that the labile Ni pool ranged from 0.9 to 32.4% (average 12.4%) of total soil Ni. Therefore the labile Ni pool in these well-equilibrated contaminated soils appears to be relatively small in relation to total Ni concentrations.

  10. Development of analytical methods for iodine speciation in fresh water

    International Nuclear Information System (INIS)

    Takaku, Yuichi; Ohtsuka, Yoshihito; Hisamatsu, Shun'ichi

    2007-01-01

    Analytical methods for physicochemical speciation of iodine in fresh water samples were developed to elucidate its behavior in the environment. The methods combined inductively coupled plasma mass spectrometry (ICP-MS) with size exclusion high performance liquid chromatography (SEC) or capillary electrophoresis (CE). Freshwater samples were collected from Lake Towada and rivers surrounding the lake. After filtration through a 0.45 μm pore size membrane filter, iodine in the water samples was pre-concentrated with an ultra-filtration filter which had a cut-off size of 10 kDa. The fraction with molecular size over 10 kDa was concentrated to 100 times in the original water, and then introduced into the SEC-ICP-MS. Molecular size chromatograms of all river and lake water samples showed two peaks for iodine concentrations: 40 kDa and 20 kDa. The method for separately determining two valence states of inorganic iodine, I - and IO 3 - , was also developed using the CE-ICP-MS system and it was successfully applied to the fresh water samples. Analysis results of surface water samples in Lake Towada and rivers surrounding the lake indicated that the chemical form of inorganic iodine in all samples was IO 3 - . Additional lake water samples were collected from Lake O-ike-higashi in the Juni-ko area at Shirakami-Sanchi, which is a UNESCO natural world heritage. The lake has a strong thermocline during all seasons; its bottom layer is in a highly reductive state. Depth profiles of I - and IO 3 - clearly showed that I - was not detected in the surface layer, but it was predominant in the bottom layer, and vice versa for IO 3 - . As this separation method is rapid and sensitive, it will be widely used in the future. (author)

  11. Speciation of phosphorus in Lake Dang of Ngaoundere-Cameroon.

    Science.gov (United States)

    Bertrand, Noumi Guy; Marie, Sieliechi Joseph; Fidèle, Fabane; Jean-Marie, Dangwang Dikdim

    2015-02-01

    In this study, we investigated the nature of phosphate phase present in sediment of Lake Dang. The phosphate speciation was determined by sequential extraction method. The concentration of phosphate in solution was measured by the ammonium molybdate method with ascorbic acid as the reducing agent. Water and sediment (surface and bottom) were sampled at eight points around the lake by taking into account activities around the lake during dry and rainy seasons. The results showed five forms of phosphorus presents in the sediments. The rank order obtained was Res-P phosphorus (P-L + P-Ca + P-Fe) than organic phase. The average phosphorus (P) content was 133, 86, and 52 μg g(-1) for the surface layer (A, 0-5 cm), medium layer (B, 5-10 cm), and bottom layer (C, 10-15 cm), respectively. This P-content depletion with depth can be explained mainly by oxygen depletion with depth which enhance P desorption. Except P-L form, the P contents were higher in rainy season compared to the dry season. The results of principal component analysis indicate that inorganic phosphorus (P-L + P-Ca + P-Fe) were linked and were provided mainly by car-washing. It appears clearly that phosphorus content vary significantly during the seasons. These results showed also that the amount of (P-Fe) is higher than the others whatever the season. This P form is easily labile and bioavailable which suggest that it can unfortunately enhance greatly the eutrophication of Lake Dang.

  12. Modelling interaction of deep groundwaters with bentonite and radionuclide speciation

    International Nuclear Information System (INIS)

    Wanner, H.

    1986-04-01

    In the safety analysis recently reported for a potential Swiss high-level waste repository, radionuclide speciation and solubility limits are calculated for expected granitic groundwater conditions. This report describes a thermodynamic model which is used to estimate the chemical composition of the pore water in compacted sodium bentonite. The model is based on available experimental data and describes the basic reactions between bentonite and groundwater by an ion-exchange model for sodium, potassium, magnesium, and calcium. The model assumes equilibrium with calcite as long as sufficient carbonates remain in the bentonite, as well as quartz saturation. The long-term situation is modelled by the assumption that the near-field of a deep repository behaves like a mixing tank. It is found that sodium bentonite will slowly be converted to calcium bentonite. The modelled composition of the pore water of compacted sodium bentonite is used to estimate radionuclide solubilities in the near-field of a deep repository. The elements considered are: uranium, neptunium, plutonium, thorium, americium, and technetium. The redox potential in the near-field is assumed to be controlled by the corrosion products of the iron canister. Except for uranium and neptunium, radionuclide solubilities turn out to be lower under the modelled near-field conditions than in the groundwater of the surrounding granitic host rock. Uranium and neptunium solubility might be higher by orders of magnitude in the near-field than in the far-field. From the chemical point of view, calcium bentonite seems to be more stable than sodium bentonite in the presence of Swiss Reference Groundwater. The use of calcium bentonite instead of sodium bentonite will improve the reliability in the prediction of source terms for radionuclide transport in the geosphere. (author)

  13. The impact of Pu speciation on distribution coefficients in Mayak soil.

    Science.gov (United States)

    Skipperud, L; Oughton, D; Salbu, B

    2000-08-10

    To assess the long-term consequences when radionuclides are released into the environment, information on the source term, transport and transformation processes, interaction with soils (KD) and biological uptake (CF) is needed. Among the artificial radionuclides released to the environment by nuclear activities, the transuranium elements are a major concern, due to very long half-lives and their accumulation in bone as well as high radiotoxicity. Plutonium has been produced in greater quantity than other transuranic elements, however, environmental assessments are complicated by the complex environmental behaviour. Physico-chemical forms of Pu will determine the interactions with soils and, thus, the degree to which soils can act as a sink or a potential diffuse source of contaminants. In the present work, dynamic tracer experiments have been performed where different Pu-species are added to a 'Mayak soil-rainwater system' to obtain information on KD values. After a defined contact time, the samples where then sequentially extracted and results are used in a dynamic box model to estimate interaction and fixation rates. The interaction of all Pu-species with soils seems to be rapid and follows a two-step reaction. Up to contact times of a few weeks, the KD for Pu(III,IV) (730 +/- 240 l/kg) is approximately one order of magnitude higher than for Pu(V,VI) (90 +/- 20 l/kg) and Pu(III,IV)-organic (40-60 l/kg). After 3 months contact time, the KD in only the two organic-bound Pu-species were significantly lower. This shows that the initial association with the soil is dependent on the Pu-species in the rainwater. After only 1 h of contact, between 33 and 40% of the plutonium was strongly bound to the soil components, i.e. only extractable with strong HNO3. The extraction of soil-bound Pu followed a similar pattern for all the original species, suggesting that the next step of Pu interaction mechanism with soil was rather independent of the original species. For both the

  14. Speciation of uranium in minerals by Sem, Tem, μ-PIXE, XPS and XAFS

    International Nuclear Information System (INIS)

    Toshihiko Ohnuki; Hiroshi Isobe; Tomihiro Kamiya; Takuro Sakai; Takashi Murakami

    2001-01-01

    Many kinds of electromagnetic waves and particle beams are used as analytical probes for the investigation of uranium-mineralogy and speciation. The representatives of the probes are SEM, TEM, μ-PIRE, XPS and XAFS. Each of these analytical probes has its own advantages and disadvantages. We have performed studies to compare the advantages and disadvantages on the basis of the analysis of the distribution and speciation of U containing rock samples collected at the Koongarra uranium deposit, Australia. The spatial resolutions of the probes are in the order of TEM>SEM, μ-PIXE>XFAS, XPS. The lower detection limits of the probes are in the order of μ-PIXE< TEM, SEM< XFAS, XPS. Oxidation state of U was determined by XFAS and XPS. These results indicate that combination of the above probes can give us sufficient data on U speciation not only in natural rock samples but in solid samples obtained in the laboratory. (authors)

  15. Speciation of Mercury in Selected Areas of the Petroleum Value Chain.

    Science.gov (United States)

    Avellan, Astrid; Stegemeier, John P; Gai, Ke; Dale, James; Hsu-Kim, Heileen; Levard, Clément; O'Rear, Dennis; Hoelen, Thomas P; Lowry, Gregory V

    2018-02-06

    Petroleum, natural gas, and natural gas condensate can contain low levels of mercury (Hg). The speciation of Hg can affect its behavior during processing, transport, and storage so efficient and safe management of Hg requires an understanding of its chemical form in oil, gas and byproducts. Here, X-ray absorption spectroscopy was used to determine the Hg speciation in samples of solid residues collected throughout the petroleum value chain including stabilized crude oil residues, sediments from separation tanks and condensate glycol dehydrators, distillation column pipe scale, and biosludge from wastewater treatment. In all samples except glycol dehydrators, metacinnabar (β-HgS) was the primary form of Hg. Electron microscopy on particles from a crude sediment showed nanosized (crude oil being processed, i.e. sweet (low sulfur crudes) vs sour (higher sulfur crudes). This information on Hg speciation in the petroleum value chain will inform development of better engineering controls and management practices for Hg.

  16. Speciation in the Derrida-Higgs model with finite genomes and spatial populations

    Science.gov (United States)

    de Aguiar, Marcus A. M.

    2017-02-01

    The speciation model proposed by Derrida and Higgs demonstrated that a sexually reproducing population can split into different species in the absence of natural selection or any type of geographic isolation, provided that mating is assortative and the number of genes involved in the process is infinite. Here we revisit this model and simulate it for finite genomes, focusing on the question of how many genes it actually takes to trigger neutral sympatric speciation. We find that, for typical parameters used in the original model, it takes the order of 105 genes. We compare the results with a similar spatially explicit model where about 100 genes suffice for speciation. We show that when the number of genes is small the species that emerge are strongly segregated in space. For a larger number of genes, on the other hand, the spatial structure of the population is less important and the species distribution overlap considerably.

  17. Transuranium element behavior in the environment: What speciation studies can tell us

    International Nuclear Information System (INIS)

    Cleveland, J.M.

    1989-01-01

    Some of the transuranium elements - especially plutonium - can exist in the environment in several different oxidation states which differ chemically from one another as much as if they were different elements. Hence an understanding of the environmental chemistry of these elements requires knowledge of their oxidation-state distribution, or speciation, under a variety of realistic conditions. Such studies are in their infancy, but already several chemical speciation methods have yielded results indicating the uniqueness of transuranic environment chemistry; for example, dioxoplutonium(V), which is unstable in the acid solutions employed in laboratory and processing plant, is often the most prevalent plutonium oxidation state in natural waters. More sensitive and less invasive physical speciation methods under development will hopefully permit the extension of these studies to a wider variety of environmental conditions and to determinations of sorbed species necessary for an understanding of sorption processes

  18. Analytical developments in ICP-MS for arsenic and selenium speciation. Application to granitic waters

    International Nuclear Information System (INIS)

    Garraud, Herve

    1999-01-01

    Nuclear waste storage in geological areas needs the understanding of the physico-chemistry of groundwaters interactions with surrounding rocks. Redox potential measurements and speciation, calculated from geochemical modelling are not significant for the determination of water reactivity. We have thus chosen to carry out experimental speciation by developing sensitive analytical tools with respect of specie chemical identity. We have studied two redox indicators from reference sites (thermal waters from Pyrenees, France): arsenic and selenium. At first, we have determined the concentrations in major ions (sulphide, sulphate, chloride, fluoride, carbonate, Na, K, Ca). Speciation was conducted by HPLC hyphenated to quadrupole ICP-MS and high resolution ICP-MS. These analyses have shown the presence of two new arsenic species in solution, in addition of a great reactivity of these waters during stability studies. A sampling, storage and analysis method is described. (author) [fr

  19. Dissolved trace metal (Cu, Cd, Co, Ni, and Ag) distribution and Cu speciation in the southern Yellow Sea and Bohai Sea, China

    Science.gov (United States)

    Li, Li; Xiaojing, Wang; Jihua, Liu; Xuefa, Shi

    2017-02-01

    Trace metals play an important role in biogeochemical cycling in ocean systems. However, because the use of trace metal clean sampling and analytical techniques has been limited in coastal China, there are few accurate trace metal data for that region. This work studied spatial distribution of selected dissolved trace metals (Ag, Cu, Co, Cd, and Ni) and Cu speciation in the southern Yellow Sea (SYS) and Bohai Sea (BS). In general, the average metal (Cu, Co, Cd, and Ni) concentrations found in the SYS were lower by a factor of two than those in BS, and they are comparable to dissolved trace metal concentrations in coastal seawater of the United States and Europe. Possible sources and sinks and physical and biological processes that influenced the distribution of these trace metals in the study region were further examined. Close relationships were found between the trace metal spatial distribution with local freshwater discharge and processes such as sediment resuspension and biological uptake. Ag, owing to its extremely low concentrations, exhibited a unique distribution pattern that magnified the influences from the physical and biological processes. Cu speciation in the water column showed that, in the study region, Cu was strongly complexed with organic ligands and concentrations of free cupric ion were in the range of 10-12.6-10-13.2 mol L-1. The distribution of Cu-complexing ligand, indicated by values of the side reaction coefficient α', was similar to the Chl a distribution, suggesting that in situ biota production may be one main source of Cu-complexing organic ligand.

  20. Speciation of Co(II) and Ni(II) in anaerobic bioreactors measured by competitive ligand exchange - adsorptive stripping voltammetry

    NARCIS (Netherlands)

    Jansen, S.; Steffen, F.; Threels, W.F.; Leeuwen, van H.P.

    2005-01-01

    Competitive ligand exchange-adsorptive stripping voltammetry is applied to speciation analysis of dissolved Ni(II) and Co(II) in an anaerobic bioreactor and similar batch media. Co and Ni speciation in these media can be measured down to concentration levels of ca. 1 nM. Sulfide interference is

  1. Use of Moessbauer spectroscopy to determine the effect of salinity on the speciation of triorganotins in Anacostia River sediments

    Energy Technology Data Exchange (ETDEWEB)

    Eng, George; Song Xueqing [University of the District of Columbia, Department of Chemistry and Physics and Agricultural Experimental Station (United States); May, Leopold, E-mail: may@cua.edu [Catholic University of America, Department of Chemistry (United States)

    2006-06-15

    The speciation of several tributyltin and triphenyltin compounds under varying salinity conditions (0, 20, 40 and 60%) was studied by Moessbauer spectroscopy in both anaerobic and aerobic Anacostia River sediments. The Moessbauer spectral parameters of the spiked sediments indicated that changes in the salinity did not affect the speciation of the tin compounds in either aerobic or anaerobic sediments.

  2. Contribution of analytical techniques coupled to the knowledge of the uranium speciation in natural conditions

    International Nuclear Information System (INIS)

    Petit, J.

    2009-06-01

    To understand the transport mechanisms and the radionuclides behaviour in the bio-geosphere is necessary to evaluate healthy and environmental risks of nuclear industry. These mechanisms are monitored by radioelements speciation, namely the distribution between their different physico-chemical forms in the environment. From this perspective, this PhD thesis deals with uranium speciation in a natural background. A detailed summary of uranium biogeochemistry has been written, which enables to restrict the PhD issue to uranium complexation with oxalic acid, a hydrophilic organic acid with good binding properties, ubiquitous in soil waters. Analytical conditions have been established by means of speciation diagrams. The speciation diagrams building by means of literature stability constants has allowed to define the analytical conditions of complex formation. The chosen analytical technique is the hyphenation of a separative technique (liquid chromatography LC or capillary electrophoresis CE) with mass spectrometry (ICPMS). The studied complexes presence in the synthetic samples has been confirmed with UV/visible spectrophotometry. LC-ICPMS analyses have proved the lability of the uranyl-organic acid complexes, namely their tendency to dissociate during analysis, which prevents from studying uranium speciation. CE-ICPMS study of labile complexes from a metal-ligand system has been made possible by employing affinity capillary electrophoresis, which enables to determine stability constants and electrophoretic mobilities. This PhD thesis has allowed to compare the different mathematical treatments of binding isotherm and to take into account ionic strength and real ligand concentration. Affinity CE has been applied successfully to lanthanum-oxalate (model system) and uranium-oxalate systems. The obtained results have been applied to a real system (situated in Le Bouchet). This shows the contribution of the developed method to the modelling of uranium speciation. (author)

  3. Chromosomal Speciation in the Genomics Era: Disentangling Phylogenetic Evolution of Rock-wallabies.

    Science.gov (United States)

    Potter, Sally; Bragg, Jason G; Blom, Mozes P K; Deakin, Janine E; Kirkpatrick, Mark; Eldridge, Mark D B; Moritz, Craig

    2017-01-01

    The association of chromosome rearrangements (CRs) with speciation is well established, and there is a long history of theory and evidence relating to "chromosomal speciation." Genomic sequencing has the potential to provide new insights into how reorganization of genome structure promotes divergence, and in model systems has demonstrated reduced gene flow in rearranged segments. However, there are limits to what we can understand from a small number of model systems, which each only tell us about one episode of chromosomal speciation. Progressing from patterns of association between chromosome (and genic) change, to understanding processes of speciation requires both comparative studies across diverse systems and integration of genome-scale sequence comparisons with other lines of evidence. Here, we showcase a promising example of chromosomal speciation in a non-model organism, the endemic Australian marsupial genus Petrogale . We present initial phylogenetic results from exon-capture that resolve a history of divergence associated with extensive and repeated CRs. Yet it remains challenging to disentangle gene tree heterogeneity caused by recent divergence and gene flow in this and other such recent radiations. We outline a way forward for better integration of comparative genomic sequence data with evidence from molecular cytogenetics, and analyses of shifts in the recombination landscape and potential disruption of meiotic segregation and epigenetic programming. In all likelihood, CRs impact multiple cellular processes and these effects need to be considered together, along with effects of genic divergence. Understanding the effects of CRs together with genic divergence will require development of more integrative theory and inference methods. Together, new data and analysis tools will combine to shed light on long standing questions of how chromosome and genic divergence promote speciation.

  4. Sample preparation and storage can change arsenic speciation in human urine.

    Science.gov (United States)

    Feldmann, J; Lai, V W; Cullen, W R; Ma, M; Lu, X; Le, X C

    1999-11-01

    Stability of chemical speciation during sample handling and storage is a prerequisite to obtaining reliable results of trace element speciation analysis. There is no comprehensive information on the stability of common arsenic species, such as inorganic arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine, in human urine. We compared the effects of the following storage conditions on the stability of these arsenic species: temperature (25, 4, and -20 degrees C), storage time (1, 2, 4, and 8 months), and the use of additives (HCl, sodium azide, benzoic acid, benzyltrimethylammonium chloride, and cetylpyridinium chloride). HPLC with both inductively coupled plasma mass spectrometry and hydride generation atomic fluorescence detection techniques were used for the speciation of arsenic. We found that all five of the arsenic species were stable for up to 2 months when urine samples were stored at 4 and -20 degrees C without any additives. For longer period of storage (4 and 8 months), the stability of arsenic species was dependent on urine matrices. Whereas the arsenic speciation in some urine samples was stable for the entire 8 months at both 4 and -20 degrees C, other urine samples stored under identical conditions showed substantial changes in the concentration of As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid. The use of additives did not improve the stability of arsenic speciation in urine. The addition of 0.1 mol/L HCl (final concentration) to urine samples produced relative changes in inorganic As(III) and As(V) concentrations. Low temperature (4 and -20 degrees C) conditions are suitable for the storage of urine samples for up to 2 months. Untreated samples maintain their concentration of arsenic species, and additives have no particular benefit. Strong acidification is not appropriate for speciation analysis.

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

    Science.gov (United States)

    Beaulieu, Jeremy M; O'Meara, Brian C

    2016-07-01

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

  6. Genetic tests for ecological and allopatric speciation in anoles on an island archipelago.

    Science.gov (United States)

    Thorpe, Roger S; Surget-Groba, Yann; Johansson, Helena

    2010-04-29

    From Darwin's study of the Galapagos and Wallace's study of Indonesia, islands have played an important role in evolutionary investigations, and radiations within archipelagos are readily interpreted as supporting the conventional view of allopatric speciation. Even during the ongoing paradigm shift towards other modes of speciation, island radiations, such as the Lesser Antillean anoles, are thought to exemplify this process. Geological and molecular phylogenetic evidence show that, in this archipelago, Martinique anoles provide several examples of secondary contact of island species. Four precursor island species, with up to 8 mybp divergence, met when their islands coalesced to form the current island of Martinique. Moreover, adjacent anole populations also show marked adaptation to distinct habitat zonation, allowing both allopatric and ecological speciation to be tested in this system. We take advantage of this opportunity of replicated island coalescence and independent ecological adaptation to carry out an extensive population genetic study of hypervariable neutral nuclear markers to show that even after these very substantial periods of spatial isolation these putative allospecies show less reproductive isolation than conspecific populations in adjacent habitats in all three cases of subsequent island coalescence. The degree of genetic interchange shows that while there is always a significant genetic signature of past allopatry, and this may be quite strong if the selection regime allows, there is no case of complete allopatric speciation, in spite of the strong primae facie case for it. Importantly there is greater genetic isolation across the xeric/rainforest ecotone than is associated with any secondary contact. This rejects the development of reproductive isolation in allopatric divergence, but supports the potential for ecological speciation, even though full speciation has not been achieved in this case. It also explains the paucity of anole species

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

    Science.gov (United States)

    Zuo, Xiaojun; Fu, Dafang; Li, He

    2012-11-01

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

  8. Incipient sympatric speciation in Midas cichlid fish from the youngest and one of the smallest crater lakes in Nicaragua due to differential use of the benthic and limnetic habitats?

    Science.gov (United States)

    Kautt, Andreas F; Machado-Schiaffino, Gonzalo; Torres-Dowdall, Julian; Meyer, Axel

    2016-08-01

    Understanding how speciation can occur without geographic isolation remains a central objective in evolutionary biology. Generally, some form of disruptive selection and assortative mating are necessary for sympatric speciation to occur. Disruptive selection can arise from intraspecific competition for resources. If this competition leads to the differential use of habitats and variation in relevant traits is genetically determined, then assortative mating can be an automatic consequence (i.e., habitat isolation). In this study, we caught Midas cichlid fish from the limnetic (middle of the lake) and benthic (shore) habitats of Crater Lake Asososca Managua to test whether some of the necessary conditions for sympatric speciation due to intraspecific competition and habitat isolation are given. Lake As. Managua is very small (Midas cichlids, Amphilophus tolteca. We found that fish from the limnetic habitat were more elongated than fish collected from the benthic habitat, as would be predicted from ecomorphological considerations. Stable isotope analyses confirmed that the former also exhibit a more limnetic lifestyle than the latter. Furthermore, split-brood design experiments in the laboratory suggest that phenotypic plasticity is unlikely to explain much of the observed differences in body elongation that we observed in the field. Yet, neutral markers (microsatellites) did not reveal any genetic clustering in the population. Interestingly, demographic inferences based on RAD-seq data suggest that the apparent lack of genetic differentiation at neutral markers could simply be due to a lack of time, as intraspecific competition may only have begun a few hundred generations ago.

  9. Effects of pH and Competing Anions on the Solution Speciation of Arsenic by Ion Exchange Resins

    Energy Technology Data Exchange (ETDEWEB)

    Impellitteri, Christopher A.; Ryan, JAmes A.; Al-Abed, Souhail R.; Scheckel, Kirk G.; Randall, Paul M.; Richardson, Collin A.

    2003-03-26

    Anion-exchange resins (AER) are used to differentiate As(V) and As(III) by retaining As(V) and allowing As(III) to pass through. AERs allow rapid speciation of As in the field which precludes the effects of sample preservation on As speciation. Aqueous environmental samples contain anions that may interfere with the speciation of As. This study compares the speciation of As by two commercially available AERs. A silica-based AER was selected for further study. As(V) and As(III) were passed through the AER in the presence of NO3 -, SO4 2-, HPO4 2-, Cl- and HCO3 - at pH 4, 6 and 8. Recoveries of As species in mixed systems range between 90 to 100%. Breakthrough curves for As(V) are presented which allow calculation of loading rates. HPO4 2- has the greatest effect on the speciation of As by AER.

  10. A study of copper, lead and cadmium speciation in some estuarine and coastal marine waters

    Energy Technology Data Exchange (ETDEWEB)

    Batley, G E; Gardner, D

    1978-07-01

    The significance of the measured changes in heavy metal distribution for different sampled environments was ascertained. The potential of a heavy metal speciation scheme to reflect differences in marine metal distributions was evaluated in a study of soluble copper, lead, and cadmium speciation in water samples from Port Hacking Estuary and one coastal Pacific station in Australia. In all samples, the percentages of metals associated with colloidal matter were high40-60% of total copper, 45-75% of total lead, and 15-35% of total cadmium. (1 map, 26 references, 4 tables)

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

    International Nuclear Information System (INIS)

    Kaplan, D.I.

    2000-01-01

    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

  12. Speciation, phenotypic variation and plasticity: what can endocrine disruptors tell us?

    Science.gov (United States)

    Ayala-García, Braulio; López-Santibáñez Guevara, Marta; Marcos-Camacho, Lluvia I; Fuentes-Farías, Alma L; Meléndez-Herrera, Esperanza; Gutiérrez-Ospina, Gabriel

    2013-01-01

    Phenotype variability, phenotypic plasticity, and the inheritance of phenotypic traits constitute the fundamental ground of processes such as individuation, individual and species adaptation and ultimately speciation. Even though traditional evolutionary thinking relies on genetic mutations as the main source of intra- and interspecies phenotypic variability, recent studies suggest that the epigenetic modulation of gene transcription and translation, epigenetic memory, and epigenetic inheritance are by far the most frequent reliable sources of transgenerational variability among viable individuals within and across organismal species. Therefore, individuation and speciation should be considered as nonmutational epigenetic phenomena.

  13. Speciation, Phenotypic Variation and Plasticity: What Can Endocrine Disruptors Tell Us?

    Directory of Open Access Journals (Sweden)

    Braulio Ayala-García

    2013-01-01

    Full Text Available Phenotype variability, phenotypic plasticity, and the inheritance of phenotypic traits constitute the fundamental ground of processes such as individuation, individual and species adaptation and ultimately speciation. Even though traditional evolutionary thinking relies on genetic mutations as the main source of intra- and interspecies phenotypic variability, recent studies suggest that the epigenetic modulation of gene transcription and translation, epigenetic memory, and epigenetic inheritance are by far the most frequent reliable sources of transgenerational variability among viable individuals within and across organismal species. Therefore, individuation and speciation should be considered as nonmutational epigenetic phenomena.

  14. Factors Controlling Redox Speciation of Plutonium and Neptunium in Extraction Separation Processes

    Energy Technology Data Exchange (ETDEWEB)

    Paulenova, Alena [Principal Investigator; Vandegrift, III, George F. [Collaborator

    2013-09-24

    The objective of the project was to examine the factors controlling redox speciation of plutonium and neptunium in UREX+ extraction in terms of redox potentials, redox mechanism, kinetics and thermodynamics. Researchers employed redox-speciation extractions schemes in parallel to the spectroscopic experiments. The resulting distribution of redox species w studied uring spectroscopic, electrochemical, and spectro-electrochemical methods. This work reulted in collection of data on redox stability and distribution of redox couples in the nitric acid/nitrate electrolyte and the development of redox buffers to stabilize the desired oxidation state of separated radionuclides. The effects of temperature and concentrations on the redox behavior of neptunium were evaluated.

  15. Measurement of elemental speciation by liquid chromatography -- inductively coupled plasma mass spectrometry (LC-ICP-MS) with the direct injection nebulizer (DIN)

    Energy Technology Data Exchange (ETDEWEB)

    Shum, Sam [Iowa State Univ., Ames, IA (United States)

    1993-05-01

    This thesis is divided into 4 parts: elemental speciation, speciation of mercury and lead compounds by microbore column LC-ICP-MS with direct injection nebulization, spatially resolved measurements of size and velocity distributions of aerosol droplets from a direct injection nebulizer, and elemental speciation by anion exchange and size exclusion chromatography with detection by ICP-MS with direct injection nebulization.

  16. [Biological agents].

    Science.gov (United States)

    Amano, Koichi

    2009-03-01

    There are two types of biological agents for the treatment of rheumatoid arthritis (RA); monoclonal antibodies and recombinant proteins. Among the latter, etanercept, a recombinant fusion protein of soluble TNF receptor and IgG was approved in 2005 in Japan. The post-marketing surveillance of 13,894 RA patients revealed the efficacy and safety profiles of etanercept in the Japanese population, as well as overseas studies. Abatacept, a recombinant fusion protein of CTLA4 and IgG, is another biological agent for RA. Two clinical trials disclosed the efficacy of abatacept for difficult-to-treat patients: the AIM for MTX-resistant cases and the ATTAIN for patients who are resistant to anti-TNF. The ATTEST trial suggested abatacept might have more acceptable safety profile than infliximab. These biologics are also promising for the treatment of RA for not only relieving clinical symptoms and signs but retarding structural damage.

  17. Biological preconcentrator

    Science.gov (United States)

    Manginell, Ronald P [Albuquerque, NM; Bunker, Bruce C [Albuquerque, NM; Huber, Dale L [Albuquerque, NM

    2008-09-09

    A biological preconcentrator comprises a stimulus-responsive active film on a stimulus-producing microfabricated platform. The active film can comprise a thermally switchable polymer film that can be used to selectively absorb and desorb proteins from a protein mixture. The biological microfabricated platform can comprise a thin membrane suspended on a substrate with an integral resistive heater and/or thermoelectric cooler for thermal switching of the active polymer film disposed on the membrane. The active polymer film can comprise hydrogel-like polymers, such as poly(ethylene oxide) or poly(n-isopropylacrylamide), that are tethered to the membrane. The biological preconcentrator can be fabricated with semiconductor materials and technologies.

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

    Science.gov (United States)

    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. Speciation of technetium in acidic media: effect of α radiations

    International Nuclear Information System (INIS)

    Denden, Ibtihel

    2013-01-01

    This project is part of the fundamental study of technetium speciation in highly acidic medium. The behaviour of technetium in HTFMS was carried out in the absence then in the presence of a irradiation. Given these two different conditions, spectrophotometric results of Tc(VII) reduction are similar. XAS analysis indicates the formation of a cyclic dimer of Tc(IV) complexed to triflate ligands and formulated asTc 2 O 2 (CF 3 SO 3 ) 4 (H 2 O)4. This compound is linearized to Tc(IV)-O-Tc(IV) with the increase of HTFMS concentration. At high concentration of HTFMS +98% (11.15 M), the protonated species TcO 3 (OH)(H 2 O) 2 which is formed in the absence of external ionizing radiations, is reduced to the V oxidation state under a irradiation. Structural characterization by EXAFS spectroscopy and DFT calculations suggests the formation of monomer species of Tc(V)-triflate complexes where [OTc(F 3 CSO 3 ) 2 (H 2 O)2] + and [OTc(F 3 CSO 3 ) 2 (OH) 2 ] - compounds were proposed. In concentrated H 2 SO 4 (CH 2 SO 4 ≥ 12 M), a-radiolysis experiments of Tc(VII) were performed in order to compare the radiolytic behaviour of Tc(VII) in both comparable media HTFMS and H 2 SO 4 . XANES studies show that radiolytic reduction of Tc(VII) leads to the formation of Tc(V)-Tc(VII) mixture in H 2 SO 4 13 M and just Tc(V) in 18 M of H 2 SO 4 . The analysis of EXAFS spectra is consistent with the formation of [TcO(HSO 4 ) 3 (H 2 O) 2 ] and [TcO(HSO 4 )3(H 2 O)(OH)] - monomer complexes in H 2 SO 4 13 M and [Tc(HSO 4 ) 3 (SO 4 )(H 2 O)] and [Tc(HSO 4 ) 3 (SO 4 )(OH)] - species at 18 M of H 2 SO 4 . (author)

  20. Sediment phosphorus speciation and mobility under dynamic redox conditions

    Science.gov (United States)

    Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

    2017-07-01

    Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the

  1. Mercury speciation and selenium in toothed-whale muscles

    Energy Technology Data Exchange (ETDEWEB)

    Sakamoto, Mineshi, E-mail: sakamoto@nimd.go.jp [National Institute for Minamata Disease, Hama 4058-18, Minamata, Kumamoto 867-0008 (Japan); Itai, Takaaki [Ehime University, Bunkyo 2-5, Matsuyama 790-8755 (Japan); Yasutake, Akira [National Institute for Minamata Disease, Hama 4058-18, Minamata, Kumamoto 867-0008 (Japan); Iwasaki, Toshihide [Tohoku National Fisheries Research Institute, 25-259 Shimomekurakubo, Aomori 031-0841 (Japan); Yasunaga, Genta; Fujise, Yoshihiro [Institute of Cetacean Research, 4-5 Toyomi, Tokyo 104-0055 (Japan); Nakamura, Masaaki [National Institute for Minamata Disease, Hama 4058-18, Minamata, Kumamoto 867-0008 (Japan); Murata, Katsuyuki [Akita University School of Medicine, Hondo 1-1-1, Akita 010-8543 (Japan); Man Chan, Hing [University of Ottawa, Marie-Curie, Ottawa, ON, Canada KIN 6N5 (Canada); Domingo, José L. [School of Medicine, IISPV, Universitat “Rovira i Virgili”, Reus (Spain); Marumoto, Masumi [National Institute for Minamata Disease, Hama 4058-18, Minamata, Kumamoto 867-0008 (Japan)

    2015-11-15

    Mercury accumulates at high levels in marine mammal tissues. However, its speciation is poorly understood. The main goal of this investigation was to establish the relationships among mercury species and selenium (Se) concentrations in toothed-whale muscles at different mercury levels. The concentrations of total mercury (T-Hg), methylmercury (MeHg), inorganic mercury (I-Hg) and Se were determined in the muscles of four toothed-whale species: bottlenose dolphins (n=31), Risso's dolphins (n=30), striped dolphins (n=29), and short-finned pilot whales (n=30). In each species, the MeHg concentration increased with increasing T-Hg concentration, tending to reach a plateau. In contrast, the proportion of MeHg in T-Hg decreased from 90–100% to 20–40%. The levels of T-Hg and Se showed strong positive correlations. Se/I-Hg molar ratios rapidly decreased with the increase of I-Hg and reached almost 1 in all species. These results suggested that the demethylated MeHg immediately formed Se/I-Hg equimolar complex of mercury selenide (HgSe) in their muscles. In addition, an X-ray absorption fine structure analysis (XAFS) of a bottlenose dolphin muscle confirmed that the dominant chemical form of the Se/I-Hg equimolar complex was HgSe. HgSe was mainly localized in cells near the endomysium using electron probe microanalysis (EPMA). These results suggested that the demethylated MeHg finally deposits within muscle cells of bottlenose dolphin as an inert HgSe. - Highlights: • T-Hg, MeHg, I-Hg and Se were determined in the muscles of four toothed-whales. • MeHg increased with increasing T-Hg and tended to reach a plateau in all species. • Se/I-Hg molar ratios rapidly decreased with increase of I-Hg and reached almost 1. • XAFS of bottlenose dolphin muscle confirmed that HgSe was dominant chemical form. • EPMA of bottlenose dolphin muscle showed that HgSe deposited in muscle cells.

  2. Mercury speciation and selenium in toothed-whale muscles

    International Nuclear Information System (INIS)

    Sakamoto, Mineshi; Itai, Takaaki; Yasutake, Akira; Iwasaki, Toshihide; Yasunaga, Genta; Fujise, Yoshihiro; Nakamura, Masaaki; Murata, Katsuyuki; Man Chan, Hing; Domingo, José L.; Marumoto, Masumi

    2015-01-01

    Mercury accumulates at high levels in marine mammal tissues. However, its speciation is poorly understood. The main goal of this investigation was to establish the relationships among mercury species and selenium (Se) concentrations in toothed-whale muscles at different mercury levels. The concentrations of total mercury (T-Hg), methylmercury (MeHg), inorganic mercury (I-Hg) and Se were determined in the muscles of four toothed-whale species: bottlenose dolphins (n=31), Risso's dolphins (n=30), striped dolphins (n=29), and short-finned pilot whales (n=30). In each species, the MeHg concentration increased with increasing T-Hg concentration, tending to reach a plateau. In contrast, the proportion of MeHg in T-Hg decreased from 90–100% to 20–40%. The levels of T-Hg and Se showed strong positive correlations. Se/I-Hg molar ratios rapidly decreased with the increase of I-Hg and reached almost 1 in all species. These results suggested that the demethylated MeHg immediately formed Se/I-Hg equimolar complex of mercury selenide (HgSe) in their muscles. In addition, an X-ray absorption fine structure analysis (XAFS) of a bottlenose dolphin muscle confirmed that the dominant chemical form of the Se/I-Hg equimolar complex was HgSe. HgSe was mainly localized in cells near the endomysium using electron probe microanalysis (EPMA). These results suggested that the demethylated MeHg finally deposits within muscle cells of bottlenose dolphin as an inert HgSe. - Highlights: • T-Hg, MeHg, I-Hg and Se were determined in the muscles of four toothed-whales. • MeHg increased with increasing T-Hg and tended to reach a plateau in all species. • Se/I-Hg molar ratios rapidly decreased with increase of I-Hg and reached almost 1. • XAFS of bottlenose dolphin muscle confirmed that HgSe was dominant chemical form. • EPMA of bottlenose dolphin muscle showed that HgSe deposited in muscle cells.

  3. Fine particulate matter (PM) and organic speciation of fireplace emissions

    International Nuclear Information System (INIS)

    Purvis, C.R.; McCrillis, R.C.; Kariher, P.H.

    2000-01-01

    This paper presents a summary of fireplace particle size and organic speciation data gathered to date in an ongoing project. Tests are being conducted in a residential wood combustion (RWC) laboratory on three factory-built fireplaces. RWC wood smoke particles <10 microm (PM10) consist primarily of a mixture of organic compounds that have condensed into droplets; therefore, the size distribution and total mass are influenced by temperature of the sample during its collection. During the series 1 tests (15 tests), the dilution tunnel used to cool and dilute the stack gases gave an average mixed gas temperature of 47.3 C and an average dilution ration of 4.3. Averages for the PM2.5 (particles <2.5 microm) and PM10 fractions were 74 and 84%, respectively. For the series 2 tests, the dilution tunnel was modified, reducing the average mixed gas temperatures to 33.8 C and increasing the average dilution ratio to 11.0 in tests completed to date. PM2.5 and PM10 fractions were 83 and 91%, respectively. Since typical winter-time mixed gas temperatures would usually be less than 10 C, these size fraction results probably represent the lower bound; the PM10 and PM2.5 size fraction results might be higher at typical winter temperatures. The particles collected on the first stage were light gray and appeared to include inorganic ash. Particles collected on the remainder of the stages were black and appeared to be condensed organics because there was noticeable lateral bleeding of the collected materials into the filter substrate. Total particulate emission rates ranged from 10.3 to 58.4 g/h; corresponding emission factors ranged from 3.3 to 14.9 g/kg of dry wood burned. A wide range of Environmental Protection Agency (EPA) Method 8270 semivolatile organic compounds were found in the emissions; of the 17 target compounds quantified, major constituents are phenol, 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol, and naphthalene

  4. Environmental biology

    International Nuclear Information System (INIS)

    Tschumi, P.A.

    1981-01-01

    Environmental biology illustrates the functioning of ecosystems and the dynamics of populations with many examples from limnology and terrestrial ecology. On this basis, present environmental problems are analyzed. The present environmental crisis is seen as a result of the failure to observe ecological laws. (orig.) [de

  5. Biological timekeeping

    DEFF Research Database (Denmark)

    Lloyd, David

    2016-01-01

    , the networks that connect differenttime domains and the oscillations, rhythms and biological clocks that coordinate andsynchronise the complexity of the living state.“It is the pattern maintained by this homeostasis, which is the touchstone ofour personal identity. Our tissues change as we live: the food we...

  6. Scaffolded biology.

    Science.gov (United States)

    Minelli, Alessandro

    2016-09-01

    Descriptions and interpretations of the natural world are dominated by dichotomies such as organism vs. environment, nature vs. nurture, genetic vs. epigenetic, but in the last couple of decades strong dissatisfaction with those partitions has been repeatedly voiced and a number of alternative perspectives have been suggested, from perspectives such as Dawkins' extended phenotype, Turner's extended organism, Oyama's Developmental Systems Theory and Odling-Smee's niche construction theory. Last in time is the description of biological phenomena in terms of hybrids between an organism (scaffolded system) and a living or non-living scaffold, forming unit systems to study processes such as reproduction and development. As scaffold, eventually, we can define any resource used by the biological system, especially in development and reproduction, without incorporating it as happens in the case of resources fueling metabolism. Addressing biological systems as functionally scaffolded systems may help pointing to functional relationships that can impart temporal marking to the developmental process and thus explain its irreversibility; revisiting the boundary between development and metabolism and also regeneration phenomena, by suggesting a conceptual framework within which to investigate phenomena of regular hypermorphic regeneration such as characteristic of deer antlers; fixing a periodization of development in terms of the times at which a scaffolding relationship begins or is terminated; and promoting plant galls to legitimate study objects of developmental biology.

  7. Biological digestion

    International Nuclear Information System (INIS)

    Rosevear, A.

    1988-01-01

    This paper discusses the biological degradation of non-radioactive organic material occurring in radioactive wastes. The biochemical steps are often performed using microbes or isolated enzymes in combination with chemical steps and the aim is to oxidise the carbon, hydrogen, nitrogen and sulphur to their respective oxides. (U.K.)

  8. Marine Biology

    Science.gov (United States)

    Dewees, Christopher M.; Hooper, Jon K.

    1976-01-01

    A variety of informational material for a course in marine biology or oceanology at the secondary level is presented. Among the topics discussed are: food webs and pyramids, planktonic blooms, marine life, plankton nets, food chains, phytoplankton, zooplankton, larval plankton and filter feeders. (BT)

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

    Science.gov (United States)

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

  10. Exceptional Chromosomal Evolution and Cryptic Speciation of Blind Mole Rats Nannospalax leucodon (Spalacinae, Rodentia from South-Eastern Europe

    Directory of Open Access Journals (Sweden)

    Ivo Savić

    2017-10-01

    Full Text Available Mole rats are exclusively subterranean and highly specialized rodents. Their long lifespans, remarkable anti-cancer mechanisms, and various distinctive adaptive features make them a useful research model. Moreover, opposing convergence of morphological traits, they have developed extremely high karyotype variability. Thus, 74 chromosomal forms have been described so far and new ones are being revealed continuously. These evolved during the process of rapid radiation and occur in different biogeographical regions. During research into their reproductive biology we have already provided substantial evidence for species-level separation of these taxa. Here, we review diverse chromosomal forms of the lesser blind mole rat, Mediterranean Nannospalax leucodon, distributed in South-eastern Europe, their karyotype records, biogeography, origin, and phylogeny from our extensive research. In the light of new data from molecular genetic studies, we question some former valuations and propose a cryptospecies rank for seven reproductively isolated chromosomal forms with sympatric and parapatric distribution and clear ecogeographical discrepances in their habitats, as well as new experimental and theoretical methods for understanding the courses of speciation of these unique fossorial mammals.

  11. Speciation evolution of zinc and copper during pyrolysis and hydrothermal carbonization treatments of sewage sludges.

    Science.gov (United States)

    Huang, Rixiang; Zhang, Bei; Saad, Emily M; Ingall, Ellery D; Tang, Yuanzhi

    2018-04-01

    Thermal and hydrothermal treatments are promising techniques for sewage sludge management that can potentially facilitate safe waste disposal, energy recovery, and nutrient recovery/recycling. Content and speciation of heavy metals in the treatment products affect the potential environmental risks upon sludge disposal and/or application of the treatment products. Therefore, it is important to study the speciation transformation of heavy metals and the effects of treatment conditions. By combining synchrotron X-ray spectroscopy/microscopy analysis and sequential chemical extraction, this study systematically characterized the speciation of Zn and Cu in municipal sewage sludges and their chars derived from pyrolysis (a representative thermal treatment technique) and hydrothermal carbonization (HTC; a representative hydrothermal treatment technique). Spectroscopy analysis revealed enhanced sulfidation of Zn and Cu by anaerobic digestion and HTC treatments, as compared to desulfidation by pyrolysis. Overall, changes in the chemical speciation and matrix properties led to reduced mobility of Zn and Cu in the treatment products. These results provide insights into the reaction mechanisms during pyrolysis and HTC treatments of sludges and can help evaluate the environmental/health risks associated with the metals in the treatment products. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Laser-induced photoacoustic spectroscopy for the speciation of transuranic elements in natural aquatic systems

    International Nuclear Information System (INIS)

    Kim, J.I.; Stumpe, R.; Klenze, R.

    1990-08-01

    Laser-induced Photoacoustic Spectroscopy (LPAS) is a new elegant instrumentation for the chemical speciation of acoustic transuranium (TRU) ions in very dilute concentrations (> 10 -8 mol L -1 ). The paper describes the principle of LPAS and its application to the study of the chemical behaviour of TRU ions in natural aquatic systems, the knowledge of which has become increasingly in demand in connection with the safety analysis of nuclear waste disposal in the geosphere. The first part of the paper describes the principle, instrumentation and characteristics of LPAS in aqueous solution, taking particular examples from our own experience. The theoretical estimation of the speciation sensitivity is demonstrated and the result is compared with experiment. The second part deals with the spectral work in aqueous solution and then with the aplication of LPAS for the speciation of TRU ions in groundwater. Some examples demonstrated are hydrolysis reaction, complexation and colloid generation of the Am 3+ ion. Speciation sensitivities of U, Np, Pu and Am of different oxidation states in a variety of aqueous solutions are summarized. The application is of course open to a broad field of microchemistry in which the conventional spectrophotometric method has difficulty with sensitivity. (orig.)

  13. First insights in the Eu(III) speciation in plant cell suspension cultures

    Energy Technology Data Exchange (ETDEWEB)

    Moll, Henry; Sachs, Susanne [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    More than 80 % of the initial Eu(III) amount was associated on Brassica napus cells after an incubation time of 24 h. The spectroscopic speciation of the cell-bound Eu(III) is characterized by an increased intensity of the {sup 7}F{sub 2} transition and prolonged luminescence lifetimes.

  14. Plant invasion and speciation along elevational gradients on the oceanic island La Palma, Canary Islands

    DEFF Research Database (Denmark)

    Steinbauer, Manuel; Irl, Severin David Howard; González-Mancebo, Juana Maria

    2017-01-01

    and anthropogenic filters, thus controlling the dispersal and establishment of species. Here, we investigate speciation and invasion processes along elevational gradients. Methods: We assess the vascular plant species richness as well as the number and percentage of endemic species and non-native species...

  15. The genetic signature of recent speciation in manta rays (Manta alfredi and M. birostris).

    Science.gov (United States)

    Kashiwagi, Tom; Marshall, Andrea D; Bennett, Michael B; Ovenden, Jennifer R

    2012-07-01

    Manta rays have been taxonomically revised as two species, Manta alfredi and M. birostris, on the basis of morphological and meristic data, yet the two species occur in extensive mosaic sympatry. We analysed the genetic signatures of the species boundary using a portion of the nuclear RAG1 (681 base pairs), mitochondrial CO1 (574 bp) and ND5 genes (1188 bp). The assay with CO1 sequences, widely used in DNA barcoding, failed to distinguish the two species. The two species were clearly distinguishable, however, with no shared RAG1 or ND5 haplotypes. The species were reciprocally monophyletic for RAG1, but paraphyletic for ND5 sequences. Qualitative evidence and statistical inferences using the 'Isolation-with-Migration models' indicated that these results were better explained with post-divergence gene flow in the recent past rather than incomplete lineage sorting with zero gene flow since speciation. An estimate of divergence time was less than 0.5 Ma with an upper confidence limit of within 1 Ma. Recent speciation of highly mobile species in the marine environment is of great interest, as it suggests that speciation may have occurred in the absence of long-term physical barriers to gene flow. We propose that the ecologically driven forces such as habitat choice played a significant role in speciation in manta rays. Copyright © 2012 Elsevier Inc. All rights reserved.

  16. Recent rapid speciation and ecomorph divergence in Indo-Australian sea snakes. Molecular Evolution

    DEFF Research Database (Denmark)

    Sanders, Kate L.; Redsted Rasmussen, Arne; Mumpuni

    2013-01-01

    The viviparous sea snakes (Hydrophiinae) are a young radiation of at least 62 species that display spectacular morphological diversity and high levels of local sympatry. To shed light on the mechanisms underlying sea snake diversification, we investigated recent speciation and eco-morphological...

  17. Ecological hybrid speciation in central-European species of Bolboschoenus: genetic and morphological evaluation

    Czech Academy of Sciences Publication Activity Database

    Píšová, Soňa; Hroudová, Zdenka; Chumová, Zuzana; Fér, T.

    2017-01-01

    Roč. 89, č. 1 (2017), s. 17-39 ISSN 0032-7786 R&D Projects: GA ČR GB14-36079G Institutional support: RVO:67985939 Keywords : AFLP * Bolboschoenus * central Europe * speciation * model-based clustering * morfometrics Subject RIV: EF - Botanics OBOR OECD: Plant sciences, botany Impact factor: 3.000, year: 2016

  18. First insights in the Eu(III) speciation in plant cell suspension cultures

    International Nuclear Information System (INIS)

    Moll, Henry; Sachs, Susanne

    2017-01-01

    More than 80 % of the initial Eu(III) amount was associated on Brassica napus cells after an incubation time of 24 h. The spectroscopic speciation of the cell-bound Eu(III) is characterized by an increased intensity of the "7F_2 transition and prolonged luminescence lifetimes.

  19. Fe (III) speciation in the high nutrient, low chlorophyll Pacific region of the Southern Ocean

    NARCIS (Netherlands)

    Nolting, R.F.; Gerringa, L.J.A.; Swagerman, M.J.W.; Timmermans, K.R.; Baar, H.J.W. de

    1998-01-01

    Fe speciation was measured with competitive ligand equilibration adsorptive cathodic stripping voltammetry in the Pacific part of the Southern Ocean between 58° and 68°30′S along the 90°W meridian. The conditional stability constant (K′ with respect to [Fe3+]) was between 10^20.6 and 10^21.6 when

  20. Speciation and demographic history of Atlantic eels (Anguilla anguilla and A. rostrata) revealed by mitogenome sequencing

    DEFF Research Database (Denmark)

    Jacobsen, M.W.; Pujolar, J.M.; Gilbert, M.T.P.

    2014-01-01

    Processes leading to speciation in oceanic environments without obvious physical barriers remain poorly known. European and American eel (Anguilla anguilla and A. rostrata) spawn in partial sympatry in the Sargasso Sea. Larvae are advected by the Gulf Stream and other currents towards the Europea...

  1. Plant speciation in continental island floras as exemplified by Nigella in the Aegean Archipelago

    OpenAIRE

    Comes, Hans Peter; Tribsch, Andreas; Bittkau, Christiane

    2008-01-01

    Continental shelf island systems, created by rising sea levels, provide a premier setting for studying the effects of geographical isolation on non-adaptive radiation and allopatric speciation brought about by genetic drift. The Aegean Archipelago forms a highly fragmented complex of mostly continental shelf islands that have become disconnected from each other and the mainland in relatively recent geological times (ca

  2. [Speciation and Risk Characteristics of Heavy Metals in the Sediments of the Yangtze Estuary].

    Science.gov (United States)

    Yin, Su; Feng, Cheng-hong; Li, Yang-yang; Yin, Li-feng; Shen, Zhen-yao

    2016-03-15

    Based on the investigation on the distribution of total contents and speciation of 8 heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) in the surface sediments at 14 typical sites of the Yangtze Estuary during three hydrological seasons ( wet, normal, and dry seasons) , this study applied equilibrium partitioning approach to build the sediment quality guidelines (SQGs) of the Yangtze Estuary, and assessed ecological risks of the heavy metals. The relationship between ecological risk and speciation of heavy metals was also revealed. The results showed that, except for Cd, the residual fraction was the main speciation of heavy metals, especially for As, Cr and Hg, their residual fraction proportions were all over 90%. The sediment quality guidelines of the Yangtze Estuary for As, Cd, Cr, Cu, Hg, Ni, Pb, Zn were 43.29, 0.672, 79.65, 19.08, 0.569, 339.09, 30.87, 411.36 µg · g⁻¹, respectively. Cu had the highest ecological risk to aquatic organisms. The upstream of Yangtze Estuary was mainly affected by Yangtze River runoff, where the risks were relatively high in wet season and relatively low in normal and dry seasons. However, the downstream of the estuary was mainly affected by municipal sewage of cities like Shanghai, where the risks were relatively high, especially in normal and dry seasons. There were three different relationships between the ecological risks and speciation of the eight heavy metals.

  3. Comparison of analytical techniques for dynamic trace metal speciation in natural freshwaters.

    NARCIS (Netherlands)

    Sigg, Laura; Black, Frank; Buffle, Jacques; Cao, Jun; Cleven, Rob; Davison, William; Galceran, Josep; Gunkel, Peggy; Kalis, Erwin; Kistler, David; Martin, Michel; Noël, Stéphane; Nur, Yusuf; Odzak, Niksa; Puy, Jaume; Riemsdijk, Willem van; Temminghoff, Erwin; Tercier-Waeber, Mary-Lou; Toepperwien, Stefanie; Town, Raewyn M; Unsworth, Emily R; Warnken, Kent W; Weng, Liping; Xue, Hanbin; Zhang, Hao

    2006-01-01

    Several techniques for speciation analysis of Cu, Zn, Cd, Pb, and Ni are used in freshwater systems and compared with respect to their performance and to the metal species detected. The analytical techniques comprise the following: (i) diffusion gradients in thin-film gels (DGT); (ii) gel integrated

  4. Speciation and Determination of Low Concentration of Iron in Beer Samples by Cloud Point Extraction

    Science.gov (United States)

    Khalafi, Lida; Doolittle, Pamela; Wright, John

    2018-01-01

    A laboratory experiment is described in which students determine the concentration and speciation of iron in beer samples using cloud point extraction and absorbance spectroscopy. The basis of determination is the complexation between iron and 2-(5-bromo-2- pyridylazo)-5-diethylaminophenol (5-Br-PADAP) as a colorimetric reagent in an aqueous…

  5. Laser-induced photoacoustic spectroscopy for the speciation of transuranic elements in natural aquatic systems

    International Nuclear Information System (INIS)

    Kim, J.I.; Stumpe, R.; Klenze, R.

    1991-01-01

    Laser-induced photoacoustic spectroscopy (LPAS) is a new elegant instrumentation for the chemical speciation of aquatic transuranium (TRU) ions in very dilute concentrations (>10 -8 mol L -1 ). The paper describes the principle of LPAS and its application to the study of the chemical behaviour of TRU ions in natural aquatic systems, the knowledge of which has become increasingly in demand in connection with the safety analysis of nuclear waste disposal in the geosphere. The first part of the paper describes the principle, instrumentation and characteristics of LPAS in aqueous solution, taking particular examples from our own experience. The theoretical estimation of the speciation sensitivity is demonstrated and the result is compared with experiment. The second part deals with the spectral work in aqueous solution and then with the application of LPAS for the speciation of TRU ions in groundwater. Some examples demonstrated are hydrolysis reaction, complexation and colloid generation of the Am 3+ ion. Speciation sensitivities of U, Np, Pu and Am of different oxidation states in a variety of aqueous solutions are summarized. The application is of course open to a broad field of microchemistry in which the conventional spectrophotometric method has difficulty with sensitivity

  6. Status of determining transuranic nuclides speciation in aqueous solution with laser spectrometry

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun; Chen Xi; Long Haoqi; Zeng Jishu; Su Xiguang; Fan Xianhua

    2007-01-01

    The knowledge about speciation of transuranic nuclides in aqueous solution is a basis for understanding the chemical and migration behavior of transuranic nuclides in aqueous solution. The speciation of transuranic nuclides with trace concentration is complicated in near neutral aqueous solutions, including change of oxidation state, complexation and colloid generation, etc. The concentrations of transuranium in near neutral aqueous solution usually below the sensitivity range of method such as conventional absorption spectroscopy. The radioactive analysis method has a very low detection limits for radionuclides, however, it wouldn' t allow the direct measurement of the transuranic species. In contrast with these methods, laser spectroscopy is an ideal method with high sensitivity, and non-contact and non-destructive for determining the speciation of transuranic nuclides. This paper summarizes the status and application of LIPAS (Laser-induced Photoacoustic Spectrometry), LIBD (Laser-induced Breakdown Detection) and TRLFS (Time-resolved Laser Fluorescence Spectrometry) to determine the speciation of transuranic nuclides with trace concentration in aqueous solutions. (authors)

  7. In Situ Distribution And Speciation Of Toxic Copper, Nickel, And Zinc In Hydrated Roots Of Cowpea

    Science.gov (United States)

    The phytotoxicity of trace metals is of global concern due to contamination of the landscape by human activities. Using synchrotron-based X-ray fluorescence microscopy and X-ray absorption spectroscopy, the distribution and speciation of Cu, Ni, and Zn was examined in situ

  8. Chemical speciation of heavy metals in sandy soils in relation to availability and mobility

    NARCIS (Netherlands)

    Temminghoff, E.J.M.

    1998-01-01

    The environmental risk of heavy metals which are present in soil at a certain total content is highly dependent on soil properties. Chemical speciation is a comprehensive term for the distribution of heavy metals over all possible chemical forms (species) in soil solution and in the solid

  9. Iodine-129 in Seawater Offshore Fukushima: distribution, inorganic speciation, sources, and budget

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Povinec, Pavel P.; Zhang, Luyuan

    2013-01-01

    The Fukushima nuclear accident in March 2011 has released a large amount of radioactive pollutants to the environment. Of the pollutants, iodine-129 is a long-lived radionuclide and will remain in the environment for millions of years. This work first report levels and inorganic speciation of 129...

  10. Speciation and bioaccumulation in a model organism of U, Np and Am in the marine environment

    International Nuclear Information System (INIS)

    Maloubier, Melody

    2015-01-01

    The fate of natural and anthropogenic radionuclides in the environment remains a major concern in our modern nuclearized societies. Among the environmental compartments, the hydrosphere is ubiquitous and can transport compounds or elements over very long distances. The recent event of Fukushima demonstrated that the marine environment could be directly affected and this raises both scientific and societal questions. Moreover, some studies have already shown that radionuclides present in seawater can be strongly accumulated by marine organisms although their speciation is most of the time unknown. Yet this knowledge is essential to better understand the transfer mechanisms from the hydrosphere to the biosphere and to evaluate their global impact on humans. In this work, we chose to experimentally determine the speciation of three actinides in doped seawater: uranium(VI), neptunium(V) and americium(III) (and the chemical surrogate europium(III)) by coupling speciation modeling with spectroscopic tools among which Time-Resolved Laser-Induced Fluorescence (TRLIF) and X-ray Absorption Spectroscopy (XAS). Then, we have studied the accumulation process in the sponge A. cavernicola, chosen here because it is considered as a bio-monitor of heavy metal pollution. The accumulation of europium(III), americium(III) and uranium(VI) in A. cavernicola were investigated at trace and ultra-trace levels. Besides, for europium, X-ray and electronic imaging permit to localize the accumulated element in the sponge and to specify its speciation [fr

  11. Biogeography of speciation in Cenozoic marine ostracoda: the role of climatic change

    Energy Technology Data Exchange (ETDEWEB)

    Cronin, T.M.

    1985-01-01

    Evolutionary theory holds that geographic isolation of populations with its resultant reproductive isolation is an important factor in the origin of new species. Climatic change alters species' biogeography by creating and eliminating barriers that affect gene flow between populations. For benthic organisms such as shallow marine ostracodes, thermal gradients at biogeographic province boundaries and the area of continental shelf are factors affected by climatic and associated sea level changes. Studies of Cenozoic marine ostracodes show that allopatric speciation does not account for paleobiogeographic patterns of species subjected to climatic change. Studies of 127 endemic species from middle latitudes of the western Atlantic show that most speciation events in temperature and subtropical taxa are, in the zoogeographic sense, sympatric or parapatric-clinal and are induced by oceanographic changes related to climatic events rather than geographic isolation of populations. Most ostracode species in middle latitudes are adapted to frequent, cyclical climatic changes typical of these regions and originated during rare periods of major climatic transition. High-latitude arctic-subarctic genera such as Finmarchinella have circumpolar distributions. A parapatric-clinal model accounts for speciation patterns observed in some high-latitude and tropical taxa. However the dynamic nature of thermal gradients and species' biogeography during climatic change renders questionable the controversial distinction between parapatric and allopatric-peripatric speciation models.

  12. Speciation of actinides in aqueous solution by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

    International Nuclear Information System (INIS)

    Kimura, Takaumi; Kato, Yoshiharu; Meinrath, G.; Yoshida, Zenko; Choppin, G.R.

    1995-01-01

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) as a sensitive and selective method has been applied to the speciation of actinides in aqueous solution. Studies on hydrolysis and carbonate complexation of U(VI) and on determination of hydration number of Cm(III) are reported. (author)

  13. Speciation of iron and manganese in the sediments of Mandovi Estuary

    Digital Repository Service at National Institute of Oceanography (India)

    Jayakumar, D.A.; Rajendran, A.

    Several attempts have been made to study the distribution of iron and manganese in Mandovi Estuary, Goa, India. But this is the first report of its kind on the speciation of these metals in sediments from Indian waters. This study would be useful...

  14. Geochemical modelling. Whatif-AQ: a computer programme for speciation calculations

    International Nuclear Information System (INIS)

    Skytte-Jensen, B.; Jensen, H.; Nielsen, O.J.

    1985-01-01

    WHATIF-AQ is part of a family of programmes for calculations of geochemistry in the near-field of radioactive waste with temperature gradients. The computer programme presented in this report calculates speciation and saturation indices for an aqueous solution at temperatures between 0-125 0 C. This report also serves as a manual to the programme

  15. Molecular evidence of cryptic speciation in the "cosmopolitan" excavating sponge Cliona celata (Porifera, Clionaidae)

    NARCIS (Netherlands)

    Xavier, J.R.; Rachello-Dolmen, P.G.; Parra-Velandia, F.; Schönberg, C.H.L.; Breeuwer, J.A.J.; van Soest, R.W.M.

    2010-01-01

    Over the past several decades molecular tools have shown an enormous potential to aid in the clarification of species boundaries in the marine realm, particularly in morphologically simple groups. In this paper we report a case of cryptic speciation in an allegedly cosmopolitan and ecologically

  16. Investigating arsenic speciation and mobilization in sediments with DGT and DET

    DEFF Research Database (Denmark)

    Bennett, William W.; Teasdale, Peter R.; Panther, Jared G.

    2012-01-01

    Mobilization of arsenic from freshwater and estuarine sediments during the transition from oxic to anoxic conditions was investigated using recently developed diffusive sampling techniques. Arsenic speciation and Fe(II) concentrations were measured at high resolution (1-3 mm) with in situ diffusi...

  17. Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass

    NARCIS (Netherlands)

    Kalis, E.J.J.; Temminghoff, E.J.M.; Town, R.M.; Unsworth, E.R.; Riemsdijk, van W.H.

    2008-01-01

    Received for publication October 12, 2007. The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total

  18. Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass.

    Science.gov (United States)

    Kalis, Erwin J J; Temminghoff, Erwin J M; Town, Raewyn M; Unsworth, Emily R; van Riemsdijk, Willem H

    2008-01-01

    The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.

  19. The impact of Co and Ni speciation on methanogenesis in sulfidic media - Biouptake versus Metal dissolution

    NARCIS (Netherlands)

    Jansen, S.; Gonzalez-Gil, G.; Leeuwen, van H.P.

    2007-01-01

    The speciation of the trace nutrients Co(II) and Ni(II) in sulfide containing media can control the methanogenic activity of Methanosarcina sp., which is of importance for the optimisation of anaerobic treatment of wastewater containing methanol. To obtain more insight in the mechanistic

  20. Introduction to the EU-network on trace element speciation: preparing for the 21(st) century

    DEFF Research Database (Denmark)

    Cornelis, R.; Camara, C.; Ebdon, L.

    1999-01-01

    ; the speciation and bioavailability of trace clement species (Cr, Fe, Se), the quality of the data and new legislation in the food session; and identification of inhaled particles and the search for bioindicators for exposure to Ni and Pt in the occupational health/hygiene session. In each session about half...

  1. Chromosomal Speciation Revisited: Modes of Diversification in Australian Morabine Grasshoppers (Vandiemenella, viatica Species Group

    Directory of Open Access Journals (Sweden)

    Steven J. B. Cooper

    2011-03-01

    Full Text Available Chromosomal rearrangements can alter the rate and patterns of gene flow within or between species through a reduction in the fitness of chromosomal hybrids or by reducing recombination rates in rearranged areas of the genome. This concept, together with the observation that many species have structural variation in chromosomes, has led to the theory that the rearrangements may play a direct role in promoting speciation. Australian morabine grasshoppers (genus Vandiemenella, viatica species group are an excellent model for studying the role of chromosomal rearrangement in speciation because they show extensive chromosomal variation, parapatric distribution patterns, and narrow hybrid zones at their boundaries. This species group stimulated development of one of the classic chromosomal speciation models, the stasipatric speciation model proposed by White in 1968. Our population genetic and phylogeographic analyses revealed extensive non-monophyly of chromosomal races along with historical and on-going gene introgression between them. These findings suggest that geographical isolation leading to the fixation of chromosomal variants in different geographic regions, followed by secondary contact, resulted in the present day parapatric distributions of chromosomal races. The significance of chromosomal rearrangements in the diversification of the viatica species group can be explored by comparing patterns of genetic differentiation between rearranged and co-linear parts of the genome.

  2. Little ecological divergence associated with speciation in two African rain forest tree genera

    NARCIS (Netherlands)

    Couvreur, T.L.P.; Porter-Morgan, H.; Wieringa, J.J.; Chatrou, L.W.

    2011-01-01

    Background - The tropical rain forests (TRF) of Africa are the second largest block of this biome after the Amazon and exhibit high levels of plant endemism and diversity. Two main hypotheses have been advanced to explain speciation processes that have led to this high level of biodiversity:

  3. Chemical speciation modelling of the South Terras and Madeira Abyssal Plain natural analogue sites

    International Nuclear Information System (INIS)

    Duffield, J.R.; Xu Langqui; Williams, D.R.

    1988-11-01

    The chemical speciation of uranium has been modelled using field data from the South Terras and Madeira Abyssal Plain natural analogue sites. In general, validation is good, particularly for the Abyssal Plain model. Problems regarding uranium redox couples have been highlighted as have other areas requiring further consideration for building into the thermodynamic models. (author)

  4. Mechanisms by Which Phenotypic Plasticity Affects Adaptive Divergence and Ecological Speciation.

    Science.gov (United States)

    Nonaka, Etsuko; Svanbäck, Richard; Thibert-Plante, Xavier; Englund, Göran; Brännström, Åke

    2015-11-01

    Phenotypic plasticity is the ability of one genotype to produce different phenotypes depending on environmental conditions. Several conceptual models emphasize the role of plasticity in promoting reproductive isolation and, ultimately, speciation in populations that forage on two or more resources. These models predict that plasticity plays a critical role in the early stages of speciation, prior to genetic divergence, by facilitating fast phenotypic divergence. The ability to plastically express alternative phenotypes may, however, interfere with the early phase of the formation of reproductive barriers, especially in the absence of geographic barriers. Here, we quantitatively investigate mechanisms under which plasticity can influence progress toward adaptive genetic diversification and ecological speciation. We use a stochastic, individual-based model of a predator-prey system incorporating sexual reproduction and mate choice in the predator. Our results show that evolving plasticity promotes the evolution of reproductive isolation under diversifying environments when individuals are able to correctly select a more profitable habitat with respect to their phenotypes (i.e., adaptive habitat choice) and to assortatively mate with relatively similar phenotypes. On the other hand, plasticity facilitates the evolution of plastic generalists when individuals have a limited capacity for adaptive habitat choice. We conclude that plasticity can accelerate the evolution of a reproductive barrier toward adaptive diversification and ecological speciation through enhanced phenotypic differentiation between diverging phenotypes.

  5. Cold Temperature Effects on Speciated VOC Emissions from Modern GDI Light-Duty Vehicles 1

    Science.gov (United States)

    In this study, speciated VOC emissions were characterized from three modern GDI light-duty vehicles. The vehicles were tested on a chassis dynamometer housed in a climate-controlled chamber at two temperatures (20 and 72 °F) using the EPA Federal Test Procedure (FTP) and a portio...

  6. FUNDAMENTALS OF MERCURY SPECIATION AND CONTROL IN COAL-FIRED BOILERS

    Science.gov (United States)

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

  7. Significance of wave form parameters in stripping chronopotentiometric metal speciation analysis

    NARCIS (Netherlands)

    Town, R.M.; Leeuwen, van H.P.

    2002-01-01

    An analysis is presented of the significance of stripping chronopotentiometric (SCP) stripping peak parameters (peak potential, Ep, and peak half-width, w1/2) for determination of metal ion speciation. This study focuses on depletive SCP (low stripping current, I¿ constant), and considers the change

  8. Complete genomes of Hairstreak butterflies, their speciation, and nucleo-mitochondrial incongruence.

    Science.gov (United States)

    Cong, Qian; Shen, Jinhui; Borek, Dominika; Robbins, Robert K; Otwinowski, Zbyszek; Grishin, Nick V

    2016-04-28

    Comparison of complete genomes of closely related species enables research on speciation and how phenotype is determined by genotype. Lepidoptera, an insect order of 150,000 species with diverse phenotypes, is well-suited for such comparative genomics studies if new genomes, which cover additional Lepidoptera families are acquired. We report a 729 Mbp genome assembly of the Calycopis cecrops, the first genome from the family Lycaenidae and the largest available Lepidoptera genome. As detritivore, Calycopis shows expansion in detoxification and digestion enzymes. We further obtained complete genomes of 8 Calycopis specimens: 3 C. cecrops and 5 C. isobeon, including a dry specimen stored in the museum for 30 years. The two species differ subtly in phenotype and cannot be differentiated by mitochondrial DNA. However, nuclear genomes revealed a deep split between them. Genes that can clearly separate the two species (speciation hotspots) mostly pertain to circadian clock, mating behavior, transcription regulation, development and cytoskeleton. The speciation hotspots and their function significantly overlap with those we previously found in Pterourus, suggesting common speciation mechanisms in these butterflies.

  9. Achieving 100% efficient postcolumn hydride generation for As speciation analysis by atomic fluorescence spectrometry

    Czech Academy of Sciences Publication Activity Database

    Marschner, Karel; Musil, Stanislav; Dědina, Jiří

    2016-01-01

    Roč. 88, č. 7 (2016), s. 4041-4047 ISSN 0003-2700 R&D Projects: GA ČR GA14-23532S Institutional support: RVO:68081715 Keywords : arsenic speciation analysis * hydride generation * HPLC Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 6.320, year: 2016

  10. ESTIMATING SPECIATION AND EXTINCTION RATES FROM DIVERSITY DATA AND THE FOSSIL RECORD

    NARCIS (Netherlands)

    Etienne, Rampal S.; Apol, M. Emile F.

    Understanding the processes that underlie biodiversity requires insight into the evolutionary history of the taxa involved. Accurate estimation of speciation, extinction, and diversification rates is a prerequisite for gaining this insight. Here, we develop a stochastic birth-death model of

  11. TEMPORAL VARIABILITY IN PHYSICAL SPECIATION OF METALS DURING A WINTER RAIN-ON-SNOW EVENT

    Science.gov (United States)

    Particulate matter in urban rivers transports a significant fraction of pollutants, changes rapidly during storm events and is difficult to characterize. In this study, the physical speciation of trace metals and organic carbon in an urban river and upstream headwaters site in To...

  12. Interactions between humic acid and hematite and their effects on metal ion speciation

    NARCIS (Netherlands)

    Vermeer, A.W.P.

    1996-01-01


    The impact of toxic chemicals (like metal ions) on the environment is a phenomenon that has been recognised as a mayor problem over the last decades. The speciation of these chemicals determines whether or not a contaminated site has to be regarded as dangerous. The fate of the

  13. Nickel speciation and complexation kinetics in freshwater by ligand exchange and DPCSV

    NARCIS (Netherlands)

    Han Bin Xue,; Jansen, S.; Prasch, A.; Sigg, L.

    2001-01-01

    A technique of ligand exchange with DMG (dimethylglyoxime) and DPCSV was applied to determine Ni speciation in lake, river, and groundwater samples. The working conditions related to ligand-exchange equilibrium were optimized, and the ligand-exchange kinetics were examined. The observed

  14. Genetic linkage of distinct adaptive traits in sympatrically speciating crater lake cichlid fish

    Czech Academy of Sciences Publication Activity Database

    Fruciano, C.; Franchini, C.; Kováčová, Viera; Elmer, K.R.; Henning, F.; Meyer, A.

    2016-01-01

    Roč. 7, SEP2016 (2016), č. článku 12736. ISSN 2041-1723 R&D Projects: GA ČR GA13-06264S Institutional support: RVO:68081707 Keywords : rna-seq * ecological speciation * geometric morphometrics * morphological variation Subject RIV: BO - Biophysics Impact factor: 12.124, year: 2016

  15. Quantification of the boron speciation in alkali borosilicate glasses by electron energy loss spectroscopy

    DEFF Research Database (Denmark)

    Cheng, D.S.; Yang, G.; Zhao, Y.Q.

    2015-01-01

    developed a method based on electron energy loss spectroscopy (EELS) data acquisition and analyses, which enables determination of the boron speciation in a series of ternary alkali borosilicate glasses with constant molar ratios. A script for the fast acquisition of EELS has been designed, from which...

  16. NEARSOL - a simple program to model actinide speciation and solubility under waste disposal conditions

    International Nuclear Information System (INIS)

    Leach, S.J.; Pryke, D.C.

    1986-05-01

    A simple program, NearSol, has been written in Fortran 77 on the Harwell Central Computer to model the aqueous speciation and solubility of actinides under near-field conditions for disposal using a simple thermodynamic approach. The methodology and running of the program are described together with a worked example. (author)

  17. Dynamic speciation analysis of atrazine in aqueous latex nanoparticle dispersions using solid phase microextraction (SPME)

    NARCIS (Netherlands)

    Benhabib, K.; Town, R.M.; Leeuwen, van H.P.

    2009-01-01

    Solid phase microextraction (SPME) is applied in the dynamic speciation analysis of the pesticide atrazine in an aqueous medium containing sorbing latex nanoparticles. It is found that the overall rate of extraction of the analyte is faster than in the absence of nanoparticles and governed by the

  18. Solid phase microextraction speciation analysis of triclosan in aqueous mediacontaining sorbing nanoparticles

    NARCIS (Netherlands)

    Zielinska, K.

    2014-01-01

    Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid

  19. Speciation evolution of zinc and copper during pyrolysis and hydrothermal carbonization treatments of sewage sludges

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Rixiang; Zhang, Bei; Saad, Emily M.; Ingall, Ellery D.; Tang, Yuanzhi

    2018-04-01

    Thermal and hydrothermal treatments are promising techniques for sewage sludge management that can potentially facilitate safe waste disposal, energy recovery, and nutrient recovery/recycling. Content and speciation of heavy metals in the treatment products affect the potential environmental risks upon sludge disposal and/or application of the treatment products. Therefore, it is important to study the speciation transformation of heavy metals and the effects of treatment conditions. By combining synchrotron X-ray spectroscopy/microscopy analysis and sequential chemical extraction, this study systematically characterized the speciation of Zn and Cu in municipal sewage sludges and their chars derived from pyrolysis (a representative thermal treatment technique) and hydrothermal carbonization (HTC; a representative hydrothermal treatment technique). Spectroscopy analysis revealed enhanced sulfidation of Zn and Cu by anaerobic digestion and HTC treatments, as compared to desulfidation by pyrolysis. Overall, changes in the chemical speciation and matrix properties led to reduced mobility of Zn and Cu in the treatment products. These results provide insights into the reaction mechanisms during pyrolysis and HTC treatments of sludges and can help evaluate the environmental/health risks associated with the metals in the treatment products.

  20. Sulfur Speciation of Crude Oils by Partial Least Squares Regression Modeling of Their Infrared Spectra

    NARCIS (Netherlands)

    de Peinder, P.; Visser, T.; Wagemans, R.W.P.; Blomberg, J.; Chaabani, H.; Soulimani, F.; Weckhuysen, B.M.

    2013-01-01

    Research has been carried out to determine the feasibility of partial least-squares regression (PLS) modeling of infrared (IR) spectra of crude oils as a tool for fast sulfur speciation. The study is a continuation of a previously developed method to predict long and short residue properties of