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

Science.gov (United States)

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

2008-01-01

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

Environmental significance of copper, lead, manganese, uranium and zinc speciation in the event of contaminated waters release from the Ranger Uranium Mining Complex

International Nuclear Information System (INIS)

Noller, B.N.; Currey, N.A.

1983-01-01

The likely impact of the accidental release of tailings dam water during the dry season at the Ranger Uranium Mining Complex was examined. A speciation scheme utilising sizing by filtration and ion-exchange with Chelex 100 has given an insight into the likely partitioning of zinc, copper, lead, manganese and uranium following the addition of tailings dam water to samples from waterbodies in the vicinity of the uranium mining/milling complex. The speciation findings are discussed in terms of likely toxic effects on fish

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

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.

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

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

Limnephilid taxa revised by speciation traits: Rhadicoleptus, Isogamus, Melampophylax genera, Chaetopteryx rugulosa, Psilopteryx psorosa species groups, Drusus bolivari, Annitella kosciuszkii species complexes (Trichoptera: Limnephilidae

Directory of Open Access Journals (Sweden)

Oláh, J.

2015-06-01

Full Text Available Speciation traits of paramere, paraproct and aedeagus were applied to find initial split criteria with fine structure analysis in order to prepare diverged trait matrices for delimiting phylogenetic incipient species of unsettled limnephilid taxa in the early stages of reproductive isolation. A brief history is presented how this phenotypic taxonomic tool of the speciation traits was discovered and applied in caddisfly taxonomy. The theoretical basis was elaborated for the phenotypic speciation trait by reviewing several relevant topics in the sciences of taxonomy, molecular genetics and phylogenetics. Perspectives of integrative taxonomy is discussed in context of phenotype versus genotype, immensely complex phenotype versus phenomic challenge, taxonomic impediment versus genetic expedient, taxonomic adaptation of genetic vocabulary versus genetic sophistication and virtualization, New Systematics of Huxley and Mayr versus New Taxonomy of Wheeler. Debates on magic trait, speciation phenotype, speciation trait and super traits are discussed concluding that evolution works with phenotype and why the cryptic species concept is irrelevant. Briefly summarized how speciation traits evolve in sexual selection, through accelerated reproductive isolation with genital evolution through sex-limited speciation traits, including minor sex chromosomes. Why neutral molecular markers are blind compared to the adaptive speciation traits sensitized by fine structure analysis and backed by the potential of high-tech and high-throughput phenotyping and cyber-infrastructure broadly accessible and fed by computable phenotype descriptions. What sort of genetics could really help taxonomy to describe biodiversity of the over 100 million unknown taxa? Collecting new and re-examining old type materials deposited in various collections, the following taxonomic actions were elaborated by speciation traits. Drusus bolivari new species complex has been erected with

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.

The complex evolutionary history and phylogeography of Caridina typus (Crustacea: Decapoda): long-distance dispersal and cryptic allopatric species.

Science.gov (United States)

Bernardes, Samuel C; Pepato, Almir R; von Rintelen, Thomas; von Rintelen, Kristina; Page, Timothy J; Freitag, Hendrik; de Bruyn, Mark

2017-08-22

The evolutionary history of the old, diverse freshwater shrimp genus Caridina is still poorly understood, despite its vast distribution - from Africa to Polynesia. Here, we used nuclear and mitochondrial DNA to infer the phylogeographic and evolutionary history of C. typus, which is one of only four species distributed across the entire range of the genus. Despite this species' potential for high levels of gene flow, questions have been raised regarding its phylogeographic structure and taxonomic status. We identified three distinct lineages that likely diverged in the Miocene. Molecular dating and ancestral range reconstructions are congruent with C. typus' early dispersal to Africa, possibly mediated by the Miocene Indian Ocean Equatorial Jet, followed by back dispersal to Australasia after the Jet's closure. Furthermore, several different species delimitation methods indicate each lineage represents a distinct (cryptic) species, contradicting current morphospecies delimitation of a single C. typus taxon. The evolutionary history of C. typus lineages is complex, in which ancient oceanic current systems and (currently unrecognised) speciation events preceded secondary sympatry of these cryptic species.

Niche divergence builds the case for ecological speciation in skinks of the Plestiodon skiltonianus species complex

Science.gov (United States)

Wogan, Guinevere O.U.; Richmond, Jonathan Q.

2015-01-01

Adaptation to different thermal environments has the potential to cause evolutionary changes that are sufficient to drive ecological speciation. Here, we examine whether climate-based niche divergence in lizards of the Plestiodon skiltonianus species complex is consistent with the outcomes of such a process. Previous work on this group shows that a mechanical sexual barrier has evolved between species that differ mainly in body size and that the barrier may be a by-product of selection for increased body size in lineages that have invaded xeric environments; however, baseline information on niche divergence among members of the group is lacking. We quantified the climatic niche using mechanistic physiological and correlative niche models and then estimated niche differences among species using ordination techniques and tests of niche overlap and equivalency. Our results show that the thermal niches of size-divergent, reproductively isolated morphospecies are significantly differentiated and that precipitation may have been as important as temperature in causing increased shifts in body size in xeric habitats. While these findings alone do not demonstrate thermal adaptation or identify the cause of speciation, their integration with earlier genetic and behavioral studies provides a useful test of phenotype–environment associations that further support the case for ecological speciation in these lizards.

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.

Origin and speciation of Picea schrenkiana and Piceasmithiana in the Center Asian Highlands and Himalayas.

Science.gov (United States)

Li, Lili; Sun, Yongshuai; Zou, Jiabin; Yue, Wei; Wang, Xi; Liu, Jianquan

Elucidating the evolutionary history of current species diversity, especially trees with large effective population sizes and long generation times, is a complicated exercise confounded by gene flow and incomplete lineage sorting. In the present study, we aim to determine the origin and speciation of Picea schrenkiana and Picea smithiana using population genetic data from chloroplast (cp), mitochondrial (mt), and nuclear (nr) genomes. These two species occur in the Central Asian Highlands and Himalayas, respectively, where they are isolated from other Asian congeneric species by the Qinghai-Tibet Plateau (QTP) or adjacent deserts. Previous studies based on both morphological and molecular evidence suggest that they have contrasting phylogenetic relationships with Picea likiangensis or Picea wilsonii which are closely related and both located in the QTP. We examined genetic variation among 16 loci of three genomes from 30 populations of these four species. At both cpDNA loci and mtDNA loci, P. schrenkiana appeared to be closely related to P. likiangensis , although statistical support for this was weak. However, phylogenetic analyses and speciation tests based on the nuclear data from 11 loci provided evidence that P. schrenkiana and P. smithiana are sister species. These two species diverged around five million years ago (Mya) while the divergence between them and the P. likiangensis - P. wilsonii clade occurred about 18.4 Mya. We also detected gene flow accompanying these speciation events. Our results highlight the complex speciation histories of these alpine conifers due to interspecific gene flow and/or incomplete lineage sorting, and the importance of the early QTP uplifts in promoting the origin of these important conifer species in the Asian highlands.

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

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.

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.

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

Experimental investigation of aluminum complexing with sodium ion and of gallium and iron (III) speciation in natural solutions

International Nuclear Information System (INIS)

Diakonov, Igor

1995-01-01

The aim of this work is to acquire thermodynamic data on the aqueous complexes forming between sodium and aluminum, gallium and hydroxide, and iron (III) and hydroxide. These data will provide for a better understanding of the transport and distribution of these elements in surface and hydrothermal fluids. Stability constants of the sodium-aluminate complex (Na Al(OH) 4 deg.) were obtained from boehmite solubility measurements at temperatures from 125 to 350 deg. C in alkaline solutions containing from 0.1 to 1 mol/L sodium. Complementary potentiometric measurements were performed with a sodium selective electrode, between 75 and 200 deg C (the potentiometric study was carried out by Gleb Pokrovski). Analyses of these data within the framework of the revised Helgeson-Kirkham-Flowers (HKF) model allowed determination of the HKF parameters for Na Al(OH) 4 deg. and calculation of its thermodynamic properties to 800 deg. C and 5 kb. The results of this work show that Na Al(OH) 4 deg. complex formation increases significantly the solubility of aluminum-bearing minerals and consequently aluminum mobility in hydrothermal fluids. Gallium speciation in surface and hydrothermal fluids is dominated by the negatively charged species, Ga(OH) 4 - . The thermodynamic properties of this species were determined from of OEGaOOH solubility measurements as a function of pH and temperature from 25 to 250 deg. C. In general, the variation of gallium aqueous speciation with pH is similar to that of aluminum other than at temperatures less than 200 deg. C over the pH range 3 - 6. This difference can account for the independent behavior of gallium versus aluminum in numerous low temperature natural systems. The thermodynamic properties of Fe(OH) 3 deg. which dominates the speciation of Fe(III) in surface waters and Fe(OH) 4 - were determined from hematite solubility measurements as a function of pH, oxygen pressure and temperature from 110 to 300 deg. C. The available thermodynamic data on

Effects of pH on the speciation of radionuclides in groundwater of beishan area, gansu province, China

International Nuclear Information System (INIS)

Zhanshi, Zhang; Wenbin, Zhou; Xianhua, Fan

2002-01-01

Speciation of radioactive nuclides is one of the most important factors in the study of migration and precipitation of the nuclides related to deep geological disposal of high level radwastes (HLW). Theoretical speciation analysis with thermodynamic equilibrium codes is an effective method. The authors have employed the EQ3NR, a computer program for geochemical aqueous speciation-solubility calculation, to evaluate the speciation of the key nuclides in the groundwater of Beishan Area, a potential area for hosting the HLW Repository of China. The calculated results showed that pH value as well as chemical composition of the water had a great impact on the speciation of key nuclides, such as Np, Pu, Am, U and Th, which would be released from HLW to the groundwater of Beishan Area. In addition, it was found that the speciation of nuclides varied from one to another. However, under alkaline conditions, the speciations were relatively simpler and hydroxyl complexes and carbonate complexes were dominant. (author)

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

Speciation in Indo-Pacific swiftlets (Aves: Apodidae): integrating molecular and phenotypic data for a new provisional taxonomy of the Collocalia esculenta complex.

Science.gov (United States)

Rheindt, Frank E; Christidis, Les; Norman, Janette A; Eaton, James A; Sadanandan, Keren R; Schodde, Richard

2017-04-07

White-bellied swiftlets of the Collocalia esculenta complex constitute a radiation of colony-breeding swifts distributed throughout the tropical Indo-Pacific region. Resolution of their taxonomy is challenging due to their morphological uniformity. To analyze the evolutionary history of this complex, we combine new biometric measurements and results from plumage assessment of museum specimens with novel as well as previously published molecular data. Together, this body of information constitutes the largest systematic dataset for white-bellied swiftlets yet compiled, drawn from 809 individuals belonging to 32 taxa for which new molecular, biometric, and/or plumage data are presented. We propose changing the classification of white-bellied swiftlets, for which two species are currently recognized, to elevate eight regional forms to species level, and we also describe two new subspecies. The ten taxa we recommend recognizing at the species level are: Collocalia linchi (Java to Lombok, Sumatran hills), C. dodgei (montane Borneo), C. natalis (Christmas Island), C. affinis (Greater Sundas, including the Thai-Malay Peninsula and Andaman-Nicobar Islands), C. marginata (Philippines), C. isonota (Philippines), C. sumbawae (west Lesser Sundas), C. neglecta (east Lesser Sundas), C. esculenta (Sulawesi, Moluccas, New Guinea, Bismarck Archipelago, Solomon Islands), and C. uropygialis (Vanuatu, New Caledonia). Future molecular and morphological work is needed to resolve questions of speciation and population affinities in the Philippines, Christmas Island, Wallacea and central Melanesia, and to shed light on historic diversification and patterns of gene flow in the complex.

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)

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)

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)

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)

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)

Speciation of binary complexes of Pb(II and Cd(II with L-asparagine in dimethyl sulfoxide - water mixtures

Directory of Open Access Journals (Sweden)

C. N. Rao

2016-02-01

Full Text Available Chemical speciation of L-Asparagine complexes of Pb(II and Cd(II in presence of (0-50% v/v dimethyl sulfoxide(DMSO-water mixtures has been studied potentiometrically at 303.0 K and at an ionic strength of 0.16 mol L-1. The models containing different number of species were refined by using the computer program MINIQUAD75. The number of species in the models is chosen based on exhaustive modeling. The predominant species formed are of the type ML2, ML2H, and ML2H2. The best fit chemical models were chosen based on statistical parameters. The convenience of the models is ascertained by studying the effect of errors in concentrations of ingredients. The trend in variation of stability constants with change in the composition of medium is explained on the basis of predominant electrostatic and non-electrostatic forces. Chemical speciation was discussed based on the distribution diagrams. DOI: http://dx.doi.org/10.4314/bcse.v30i1.6

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)

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, ...

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.

The mate recognition protein gene mediates reproductive isolation and speciation in the Brachionus plicatilis cryptic species complex.

Science.gov (United States)

Gribble, Kristin E; Mark Welch, David B

2012-08-01

Chemically mediated prezygotic barriers to reproduction likely play an important role in speciation. In facultatively sexual monogonont rotifers from the Brachionus plicatilis cryptic species complex, mate recognition of females by males is mediated by the Mate Recognition Protein (MRP), a globular glycoprotein on the surface of females, encoded by the mmr-b gene family. In this study, we sequenced mmr-b copies from 27 isolates representing 11 phylotypes of the B. plicatilis species complex, examined the mode of evolution and selection of mmr-b, and determined the relationship between mmr-b genetic distance and mate recognition among isolates. Isolates of the B. plicatilis species complex have 1-4 copies of mmr-b, each composed of 2-9 nearly identical tandem repeats. The repeats within a gene copy are generally more similar than are gene copies among phylotypes, suggesting concerted evolution. Compared to housekeeping genes from the same isolates, mmr-b has accumulated only half as many synonymous differences but twice as many non-synonymous differences. Most of the amino acid differences between repeats appear to occur on the outer face of the protein, and these often result in changes in predicted patterns of phosphorylation. However, we found no evidence of positive selection driving these differences. Isolates with the most divergent copies were unable to mate with other isolates and rarely self-crossed. Overall the degree of mate recognition was significantly correlated with the genetic distance of mmr-b. Discrimination of compatible mates in the B. plicatilis species complex is determined by proteins encoded by closely related copies of a single gene, mmr-b. While concerted evolution of the tandem repeats in mmr-b may function to maintain identity, it can also lead to the rapid spread of a mutation through all copies in the genome and thus to reproductive isolation. The mmr-b gene is evolving rapidly, and novel alleles may be maintained and increase in

The mate recognition protein gene mediates reproductive isolation and speciation in the Brachionus plicatilis cryptic species complex

Directory of Open Access Journals (Sweden)

Gribble Kristin E

2012-08-01

Full Text Available Abstract Background Chemically mediated prezygotic barriers to reproduction likely play an important role in speciation. In facultatively sexual monogonont rotifers from the Brachionus plicatilis cryptic species complex, mate recognition of females by males is mediated by the Mate Recognition Protein (MRP, a globular glycoprotein on the surface of females, encoded by the mmr-b gene family. In this study, we sequenced mmr-b copies from 27 isolates representing 11 phylotypes of the B. plicatilis species complex, examined the mode of evolution and selection of mmr-b, and determined the relationship between mmr-b genetic distance and mate recognition among isolates. Results Isolates of the B. plicatilis species complex have 1–4 copies of mmr-b, each composed of 2–9 nearly identical tandem repeats. The repeats within a gene copy are generally more similar than are gene copies among phylotypes, suggesting concerted evolution. Compared to housekeeping genes from the same isolates, mmr-b has accumulated only half as many synonymous differences but twice as many non-synonymous differences. Most of the amino acid differences between repeats appear to occur on the outer face of the protein, and these often result in changes in predicted patterns of phosphorylation. However, we found no evidence of positive selection driving these differences. Isolates with the most divergent copies were unable to mate with other isolates and rarely self-crossed. Overall the degree of mate recognition was significantly correlated with the genetic distance of mmr-b. Conclusions Discrimination of compatible mates in the B. plicatilis species complex is determined by proteins encoded by closely related copies of a single gene, mmr-b. While concerted evolution of the tandem repeats in mmr-b may function to maintain identity, it can also lead to the rapid spread of a mutation through all copies in the genome and thus to reproductive isolation. The mmr-b gene is evolving

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...

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

Genetic variability, local selection and demographic history: genomic evidence of evolving towards allopatric speciation in Asian seabass.

Science.gov (United States)

Wang, Le; Wan, Zi Yi; Lim, Huan Sein; Yue, Gen Hua

2016-08-01

Genomewide analysis of genetic divergence is critically important in understanding the genetic processes of allopatric speciation. We sequenced RAD tags of 131 Asian seabass individuals of six populations from South-East Asia and Australia/Papua New Guinea. Using 32 433 SNPs, we examined the genetic diversity and patterns of population differentiation across all the populations. We found significant evidence of genetic heterogeneity between South-East Asian and Australian/Papua New Guinean populations. The Australian/Papua New Guinean populations showed a rather lower level of genetic diversity. FST and principal components analysis revealed striking divergence between South-East Asian and Australian/Papua New Guinean populations. Interestingly, no evidence of contemporary gene flow was observed. The demographic history was further tested based on the folded joint site frequency spectrum. The scenario of ancient migration with historical population size changes was suggested to be the best fit model to explain the genetic divergence of Asian seabass between South-East Asia and Australia/Papua New Guinea. This scenario also revealed that Australian/Papua New Guinean populations were founded by ancestors from South-East Asia during mid-Pleistocene and were completely isolated from the ancestral population after the last glacial retreat. We also detected footprints of local selection, which might be related to differential ecological adaptation. The ancient gene flow was examined and deemed likely insufficient to counteract the genetic differentiation caused by genetic drift. The observed genomic pattern of divergence conflicted with the 'genomic islands' scenario. Altogether, Asian seabass have likely been evolving towards allopatric speciation since the split from the ancestral population during mid-Pleistocene. © 2016 John Wiley & Sons Ltd.

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)

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

Correlation of retention of lanthanide and actinide complexes with stability constants and their speciation

Energy Technology Data Exchange (ETDEWEB)

Datta, A.; Sivaraman, N.; Viswanathan, K.S.; Ghosh, Suddhasattwa; Srinivasan, T.G.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2013-03-01

The present study describes a correlation that is developed from retention of lanthanide and actinide complexes with the stability constant. In these studies, an ion-pairing reagent, camphor-10-sulphonic acid (CSA) was used as the modifier and organic acids such as {alpha}-hydroxy isobutyric acid ({alpha}-HIBA), mandelic acid, lactic acid and tartaric acid were used as complexing reagent for elution. From these studies, a correlation has been established between capacity factor of a metal ion, concentration of ion-pairing reagent and complexing agent with the stability constant of metal complex. Based on these studies, it has been shown that the stability constant of lanthanide and actinide complexes can be estimated using a single lanthanide calibrant. Validation of the method was carried out with the complexing agents such as {alpha}-HIBA and lactic acid. It was also demonstrated that data from a single chromatogram can be used for estimation of stability constant at various ionic strengths. These studies also demonstrated that the method can be applied for estimation of stability constant of actinides with a ligand whose value is not reported yet, e.g., ligands of importance in the lanthanide-actinide separations, chelation therapy etc. The chromatographic separation method is fast and the estimation of stability constant can be done in a very short time, which is a significant advantage especially in dealing with radioactive elements. The stability constant data was used to derive speciation data of plutonium in different oxidation states as well as that of americium with {alpha}-HIBA. The elution behavior of actinides such as Pu and Am from reversed phase chromatographic technique could be explained based on these studies. (orig.)

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

Self-assembly of a helical zinc-europium complex: speciation in aqueous solution and luminescence

Directory of Open Access Journals (Sweden)

Emmanuel eDeiters

2013-09-01

Full Text Available Two new tridentate(NNO-bidentate(NN compartmental ligands, HL5 and HL6, are synthesized from pyridine and benzimidazole synthons. They react in aqueous solution under physiological conditions with ZnII, LnIII, or a mixture thereof, to yield complexes of different stoichiometries, 1:3, 2:2, 2:3, 1:1:3, the speciation of which is established by UV-visible titrations and ESI mass spectrometry. Photophysical studies of the EuIII-containing solutions in Tris-HCl 0.1 M (pH = 7.4 show that lanthanide luminescence arises from a unique N6O3 coordination site with pseudo D3 symmetry. Relevant parameters such as crystal field splitting, lifetime, radiative lifetime and intrinsic quantum yield perfectly match those reported for dinuclear 4f-4f helicates in which the EuIII ion has the same coordination environment.

On the use of time-resolved laser-induced fluorescence (TRLIF) and electrospray mass spectrometry (ES-MS) for speciation studies

International Nuclear Information System (INIS)

Moulin, C.

2003-01-01

Time-resolved laser induced fluorescence (TRLIF) and electrospray mass spectrometry (ES-MS) are used for speciation studies. While the former has been used for long time, the latter is rather new in the field of speciation. These two techniques have different advantages such as sensitivity (especially for TRLIF), selectivity and multielement capabilities (in case of ES-MS). Examples obtained from studies carried out within the CEA are presented. Concerning TRLIF, emphasis is put on uranyl ion speciation in nitric acid to phosphoric acid going through hydroxo complexes. Concerning ES-MS, humic substances identification as well as speciation of cesium, zirconium, thorium and uranyl ions in various complexing media are presented. Comparisons of TRLIF and ES-MS results are made in the case of uranyl hydroxo complexes and favourably compared with OECD data. Trends for these two techniques are also discussed. (orig.)

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

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

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.)

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...

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

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)

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)

Genome size evolution at the speciation level: the cryptic species complex Brachionus plicatilis (Rotifera).

Science.gov (United States)

Stelzer, Claus-Peter; Riss, Simone; Stadler, Peter

2011-04-07

Studies on genome size variation in animals are rarely done at lower taxonomic levels, e.g., slightly above/below the species level. Yet, such variation might provide important clues on the tempo and mode of genome size evolution. In this study we used the flow-cytometry method to study the evolution of genome size in the rotifer Brachionus plicatilis, a cryptic species complex consisting of at least 14 closely related species. We found an unexpectedly high variation in this species complex, with genome sizes ranging approximately seven-fold (haploid '1C' genome sizes: 0.056-0.416 pg). Most of this variation (67%) could be ascribed to the major clades of the species complex, i.e. clades that are well separated according to most species definitions. However, we also found substantial variation (32%) at lower taxonomic levels--within and among genealogical species--and, interestingly, among species pairs that are not completely reproductively isolated. In one genealogical species, called B. 'Austria', we found greatly enlarged genome sizes that could roughly be approximated as multiples of the genomes of its closest relatives, which suggests that whole-genome duplications have occurred early during separation of this lineage. Overall, genome size was significantly correlated to egg size and body size, even though the latter became non-significant after controlling for phylogenetic non-independence. Our study suggests that substantial genome size variation can build up early during speciation, potentially even among isolated populations. An alternative, but not mutually exclusive interpretation might be that reproductive isolation tends to build up unusually slow in this species complex.

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

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing.

Science.gov (United States)

Tandy, Susan; Ammann, Adrian; Schulin, Rainer; Nowack, Bernd

2006-07-01

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.

Phylogenetic and population genetic analyses of diploid Leucaena (Leguminosae; Mimosoideae) reveal cryptic species diversity and patterns of divergent allopatric speciation.

Science.gov (United States)

Govindarajulu, Rajanikanth; Hughes, Colin E; Bailey, C Donovan

2011-12-01

Leucaena comprises 17 diploid species, five tetraploid species, and a complex series of hybrids whose evolutionary histories have been influenced by human seed translocation, cultivation, and subsequent spontaneous hybridization. Here we investigated patterns of evolutionary divergence among diploid Leucaena through comprehensively sampled multilocus phylogenetic and population genetic approaches to address species delimitation, interspecific relationships, hybridization, and the predominant mode of speciation among diploids. Parsimony- and maximum-likelihood-based phylogenetic approaches were applied to 59 accessions sequenced for six SCAR-based nuclear loci, nrDNA ITS, and four cpDNA regions. Population genetic comparisons included 1215 AFLP loci representing 42 populations and 424 individuals. Phylogenetic results provided a well-resolved hypothesis of divergent species relationships, recovering previously recognized clades of diploids as well as newly resolved relationships. Phylogenetic and population genetic assessments identified two cryptic species that are consistent with geography and morphology. Findings from this study highlight the importance and utility of multilocus data in the recovery of complex evolutionary histories. The results are consistent with allopatric divergence representing the predominant mode of speciation among diploid Leucaena. These findings contrast with the potential hybrid origin of several tetraploid species and highlight the importance of human translocation of seed to the origin of these tetraploids. The recognition of one previously unrecognized species (L. cruziana) and the elevation of another taxon (L. collinsii subsp. zacapana) to specific status (L. zacapana) is consistent with a growing number of newly diagnosed species from neotropical seasonally dry forests, suggesting these communities harbor greater species diversity than previously recognized.

Magadi tilapia ecological specialization: filling the early gap in the speciation continuum.

Science.gov (United States)

Pinho, Catarina; Faria, Rui

2016-04-01

Cichlid fish are well known for their high speciation rates, which are usually accompanied by spectacular and rapid diversification in eco-morphological and secondary sexual traits. This is best illustrated by the famous repeated explosive radiations in the African Great Lakes Tanganyika, Malawi and Victoria, each lake harbouring several hundreds of mostly endemic species. Correspondingly, cichlids diversified very rapidly in many other lakes across their range. Although the larger radiations, unparalleled in vertebrates, are certainly the most intriguing, they are also the most intricate and difficult to address because of their complex nature. This is where smaller, simpler systems may prove to be the most useful. In this issue of Molecular Ecology, Kavembe et al. (2016) report very recent genetic diversification accompanied by ecological specialization in cichlids of the small and ecologically extreme Lake Magadi, in Kenya. Combining geometric morphometrics, stable isotope analysis, population genomics using RADSeq data and coalescent-based modelling techniques, the authors characterize the eco-morphological differences between genetically distinct populations of Magadi tilapia (Alcolapia grahami), which are consistent with the different environmental conditions they experience, and infer their history of divergence. The simplicity of the focal system and the use of a multidisciplinary approach make this work particularly important for our understanding of the early stages of speciation, in both cichlids and other organisms. © 2016 John Wiley & Sons Ltd.

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.)

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)

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters

Energy Technology Data Exchange (ETDEWEB)

Jones, Adele M.; Xue, Youjia [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Kinsela, Andrew S. [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia); Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Wilcken, Klaus M. [Institute for Environmental Research (IER), Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234 (Australia); Collins, Richard N., E-mail: richard.collins@unsw.edu.au [School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW 2052 (Australia)

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values < 3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with {sup 55}Fe and {sup 26}Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (> 70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO{sub 4}){sub 2}{sup −} and/or Me–NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. - Highlights: • CLASS discharge large amounts of metals and their speciation is poorly

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.

Genome size evolution at the speciation level: The cryptic species complex Brachionus plicatilis (Rotifera

Directory of Open Access Journals (Sweden)

Riss Simone

2011-04-01

Full Text Available Abstract Background Studies on genome size variation in animals are rarely done at lower taxonomic levels, e.g., slightly above/below the species level. Yet, such variation might provide important clues on the tempo and mode of genome size evolution. In this study we used the flow-cytometry method to study the evolution of genome size in the rotifer Brachionus plicatilis, a cryptic species complex consisting of at least 14 closely related species. Results We found an unexpectedly high variation in this species complex, with genome sizes ranging approximately seven-fold (haploid '1C' genome sizes: 0.056-0.416 pg. Most of this variation (67% could be ascribed to the major clades of the species complex, i.e. clades that are well separated according to most species definitions. However, we also found substantial variation (32% at lower taxonomic levels - within and among genealogical species - and, interestingly, among species pairs that are not completely reproductively isolated. In one genealogical species, called B. 'Austria', we found greatly enlarged genome sizes that could roughly be approximated as multiples of the genomes of its closest relatives, which suggests that whole-genome duplications have occurred early during separation of this lineage. Overall, genome size was significantly correlated to egg size and body size, even though the latter became non-significant after controlling for phylogenetic non-independence. Conclusions Our study suggests that substantial genome size variation can build up early during speciation, potentially even among isolated populations. An alternative, but not mutually exclusive interpretation might be that reproductive isolation tends to build up unusually slow in this species complex.

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)

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.

Organomineral Complexation at the Nanoscale: Iron Speciation and Soil Carbon Stabilization

Science.gov (United States)

Coward, E.; Thompson, A.; Plante, A. F.

2016-12-01

Much of the uncertainty in the biogeochemical behavior of soil carbon (C) in tropical ecosystems derives from an incomplete understanding of soil C stabilization processes. The 2:1 phyllosilicate clays often associated with temperate organomineral complexation are largely absent in tropical soils due to extensive weathering. In contrast, these soils contain an abundance of Fe- and Al-containing short-range-order (SRO) mineral phases capable of C stabilization through sorption or co-precipitation, largely enabled by high specific surface area (SSA). SRO-mediated organomineral associations may thus prove a critical, yet matrix-selective, driver of the long-term C stabilization capacity observed in tropical soils. Characterizing the interactions between inherently heterogeneous organic matter and amorphous mineralogy presses the limits of current analytical techniques. This work pairs inorganic selective dissolution with high-resolution assessment of Fe speciation to determine the contribution of extracted mineral phases to the mineral matrix, and to C stabilization capacity. Surface (0-20 cm) samples were taken from 20 quantitative soil pits within the Luquillo Critical Zone Observatory in northeast Puerto Rico stratified across granodioritic and volcaniclastic parent materials. 57Fe-Mössbauer spectroscopy (MBS) and x-ray diffraction (XRD) before and after Fe-SOM extraction were used to assess changes in the mineralogical matrix associated with SOM dissolution, while N2-BET sorption was used to determine the contributions of the extractable phases to SSA. Results indicate (1) selective extraction of soil C produces significant shifts in Fe phase distribution, (2) SRO minerals contribute substantially to SSA, and (3) SRO minerals appear protected by more crystalline phases via physical mechanisms, rather than dissolution-dependent chemical bonds. This nanoscale characterization of Fe-C complexes thus provides evidence for both anticipated mineral-organic and

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

Energy Technology Data Exchange (ETDEWEB)

Robinson, Troy A [Univ. of Nevada, Las Vegas, NV (United States)

2011-08-01

phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu³⁺) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu³⁺) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu³⁺ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.

Mate Choice Drives Evolutionary Stability in a Hybrid Complex.

Directory of Open Access Journals (Sweden)

Miguel Morgado-Santos

Full Text Available Previous studies have shown that assortative mating acts as a driver of speciation by countering hybridization between two populations of the same species (pre-zygotic isolation or through mate choice among the hybrids (hybrid speciation. In both speciation types, assortative mating promotes speciation over a transient hybridization stage. We studied mate choice in a hybrid vertebrate complex, the allopolyploid fish Squalius alburnoides. This complex is composed by several genomotypes connected by an intricate reproductive dynamics. We developed a model that predicts the hybrid complex can persist when females exhibit particular mate choice patterns. Our model is able to reproduce the diversity of population dynamic outcomes found in nature, namely the dominance of the triploids and the dominance of the tetraploids, depending on female mate choice patterns and frequency of the parental species. Experimental mate choice trials showed that females exhibit the preferences predicted by the model. Thus, despite the known role of assortative mating in driving speciation, our findings suggest that certain mate choice patterns can instead hinder speciation and support the persistence of hybrids over time without speciation or extinction.

The role of different network modifying cations on the speciation of the Co2 + complex in silicates and implication in the investigation of historical glasses

Science.gov (United States)

Fornacelli, Cristina; Ceglia, Andrea; Bracci, Susanna; Vilarigues, Marcia

2018-01-01

In the last decades the speciation of the cobalt complex in a glass matrix has been extensively studied. Bivalent cobalt ions in glasses of different composition commonly adopt a tetrahedral coordination, though hexa- or penta-coordinated species are also possible. Changes in the absorbance spectrum of Co-doped glasses were attested in previous studies according to the introduction of different modifying cations. A shifting of the first sub-band characterizing the typical triplets of tetrahedral Co2 + ions in both the visible and near infrared regions was observed, but discrepancies in literature suggested a relevant role of glass composition on the definition of the optical signature of cobalt. Co-doped glasses with different composition (soda-lime, potash-lime, mixed alkali and ZnO-Na2O-CaO-SiO2) were studied via Fiber Optic Reflectance Spectroscopy (FORS). Pseudo-Voigt functions were used for the deconvolution of the absorbance spectra and the features of the bands characteristic of each cobalt complex were investigated. The structural role played by each modifying cation and the fundamental implications of glass basicity on the speciation of different Co-complexes were stressed. Changes in glass structure resulted in different equilibria between the three absorbing species whose specific optical signatures in the 480-530 nm region interact to determine the resulting absorbance spectrum.

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.

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

The long term tsunami impact: Evolution of iron speciation and major elements concentration in tsunami deposits from Thailand.

Science.gov (United States)

Kozak, Lidia; Niedzielski, Przemyslaw

2017-08-01

The article describes the unique studies of the chemical composition changes of new geological object (tsunami deposits in south Thailand - Andaman Sea Coast) during four years (2005-2008) from the beginning of formation of it (deposition of tsunami transported material, 26 December 2004). The chemical composition of the acid leachable fraction of the tsunami deposits has been studied in the scope of concentration macrocompounds - concentration of calcium, magnesium, iron, manganese and iron speciation - the occurrence of Fe(II), Fe(III) and non-ionic iron species described as complexed iron (Fe complex). The changes of chemical composition and iron speciation in the acid leachable fraction of tsunami deposits have been observed with not clear tendencies of changes direction. For iron speciation changes the transformation of the Fe complex to Fe(III) has been recorded with no significant changes of the level of Fe(II). Copyright © 2017 Elsevier Ltd. All rights reserved.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

Science.gov (United States)

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Speciation, Divergence, and the Origin of Gryllus rubens: Behavior, Morphology, and Molecules

Directory of Open Access Journals (Sweden)

David A. Gray

2011-05-01

Full Text Available The last 25 years or so has seen a huge resurgence of interest in speciation research. This has coincided with the development and widespread use of new tools in molecular genetics, especially DNA sequencing, to inform ecological and evolutionary questions. Here I review about a decade of work on the sister species of field crickets Gryllus texensis and G. rubens. This work has included analysis of morphology, behavior, and the mitochondrial DNA molecule. The molecular work in particular has dramatically re-shaped my interpretation of the speciational history of these taxa, suggesting that rather than ‘sister’ species we should consider these taxa as ‘mother-daughter’ species with G. rubens derived from within a subset of ancestral G. texensis.

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.

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

Science.gov (United States)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

2017-06-01

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth's history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES) spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes-many containing organic ligands-we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H2S(aq)] < 11 μM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO3, MoOxS4-x2- (intermediate thiomolybdates), and [MoOx(cat)4-x]2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS42- (tetrathiomolybdate).

The radiolytic and chemical degradation of organic ion exchange resins under alkaline conditions: effect on radionuclide speciation

International Nuclear Information System (INIS)

Loon, L. van; Hummel, W.

1995-10-01

The formation of water soluble organic ligands by the radiolytic and chemical degradation of several ion exchange resins was investigated under conditions close to those of the near field of a cementitious repository. The most important degradation products were characterised and their role on radionuclide speciation evaluated thoroughly. Irradiation of strong acidic cation exchange resins (Powdex PCH and Lewatite S-100) resulted in the formation of mainly sulphate and dissolved organic carbon. A small part of the carbon (10-20%) could be identified as oxalate. The identity of the remainder is unknown. Complexation studies with Cu 2+ and Ni 2+ showed the presence of two ligands: oxalate and ligand X. Although ligand X could not be identified, it could be characterised by its concentration, a deprotonation constant and a complexation constant for the NiX complex. The influence of oxalate and ligand X on the speciation of radionuclides is examined in detail. For oxalate no significant influence on the speciation of radionuclides is expected. The stronger complexing ligand X may exert some influence depending on its concentration and the values of other parameters. These critical parameters are discussed and limiting values are evaluated. In absence of irradiation, no evidence for the formation of ligands was found. Irradiation of strong basic anion exchange resins (Powdex PAO and Lewatite M-500) resulted in the formation of mainly ammonia, amines and dissolved organic carbon. Up to 50% of the carbon could be identified as methyl-, dimethyl- and trimethylamine. Complexation studies with Eu 3+ showed that the complexing capacity under near field conditions was negligible. The speciation of cations such as Ag, Ni, Cu and Pd can be influenced by the presence of amins. The strongest amine-complexes are formed with Pd and therefore, as an example, the aqueous Pd-ammonia system is examined in great detail. (author) 30 figs., 10 tabs., refs

Recurrent evolution of host and vector association in bacteria of the Borrelia burgdorferi sensu lato species complex.

Science.gov (United States)

Becker, Noémie S; Margos, Gabriele; Blum, Helmut; Krebs, Stefan; Graf, Alexander; Lane, Robert S; Castillo-Ramírez, Santiago; Sing, Andreas; Fingerle, Volker

2016-09-15

The Borrelia burgdorferi sensu lato (s.l.) species complex consists of tick-transmitted bacteria and currently comprises approximately 20 named and proposed genospecies some of which are known to cause Lyme Borreliosis. Species have been defined via genetic distances and ecological niches they occupy. Understanding the evolutionary relationship of species of the complex is fundamental to explaining patterns of speciation. This in turn forms a crucial basis to frame testable hypotheses concerning the underlying processes including host and vector adaptations. Illumina Technology was used to obtain genome-wide sequence data for 93 strains of 14 named genospecies of the B. burgdorferi species complex and genomic data already published for 18 additional strain (including one new species) was added. Phylogenetic reconstruction based on 114 orthologous single copy genes shows that the genospecies represent clearly distinguishable taxa with recent and still ongoing speciation events apparent in Europe and Asia. The position of Borrelia species in the phylogeny is consistent with host associations constituting a major driver for speciation. Interestingly, the data also demonstrate that vector associations are an additional driver for diversification in this tick-borne species complex. This is particularly obvious in B. bavariensis, a rodent adapted species that has diverged from the bird-associated B. garinii most likely in Asia. It now consists of two populations one of which most probably invaded Europe following adaptation to a new vector (Ixodes ricinus) and currently expands its distribution range. The results imply that genotypes/species with novel properties regarding host or vector associations have evolved recurrently during the history of the species complex and may emerge at any time. We suggest that the finding of vector associations as a driver for diversification may be a general pattern for tick-borne pathogens. The core genome analysis presented here

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.

Radioactive contaminants in the subsurface: the influence of complexing ligands on trace metal speciation

International Nuclear Information System (INIS)

Hummel, W.

2007-01-01

in Swiss radioactive waste disposal projects. Within the scope of this TDB project I reviewed extensively thermodynamic data for Th, Pd, Al, and solubility and metal complexation of silicates, the review considering not only U, Np, Pu, Am, Tc, Ni, Se and Zr, but also the major constituents of ground and surface waters, i.e. H, Na, K, Mg and Ca. The decision to evaluate the organic ligands oxalate, citrate, ethylenediaminetetraacetate (edta) and α-isosaccharinate (isa) was based on two aspects, namely the importance of the ligands in radioactive waste problems, and the availability of experimental data. (ii) In many case studies involving inorganic and simple organic ligands a serious lack of reliable thermodynamic data is encountered. There, a new modeling approach to estimate the effects of these missing data was applied. This so called 'backdoor approach' begins with the question: 'What total concentration of a ligand is necessary to significantly influence the speciation, and hence the solubility, of a given trace metal?' Radioactive waste contains substantial amounts of ion-exchange resins from decontamination procedures. Degradation of these organic waste forms by radiolysis in a repository is a source of concern in radioactive waste management. Radiolytic degradation experiments with strong acidic ion exchange resins resulted in the formation of the complexing ligands oxalate and ligand X, whose structure could not be identified. In the case of anion exchange resins, ammonia and methylamines were detected. I assessed the influence of these ligands on radionuclide speciation in groundwater and cement pore water of a repository using the 'backdoor approach'. Prussian Blue, Fe III 4 [Fe II (CN) 6 ] 3 , and structurally related transition metal compounds like Ni 2 [Fe(CN) 6 ] are used as cesium ion exchangers in decontamination procedures of liquid radioactive waste. The used ion exchangers are conditioned as cementitious waste form for interim storage and finally

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...

Ion mobility spectrometry focusing on speciation analysis of metals/metalloids bound to carbonic anhydrase.

Science.gov (United States)

Pessôa, Gustavo de Souza; Pilau, Eduardo Jorge; Gozzo, Fábio Cesar; Arruda, Marco Aurélio Zezzi

2013-09-01

In the present work, traveling wave ion mobility spectrometry-mass spectrometry (TWIMS-MS) was applied to speciation analysis of metalloproteins. The influence of pH on complexation conditions between some metals and bovine carbonic anhydrase was evaluated from pH 6 to 9, as well as the time involved in their complexation (0-24 h). Employing TWIMS-MS, two conformational states of bovine carbonic anhydrase were observed with charge states of +12 and +11; these configurations being evaluated in terms of the folded state of the apo form and this protein (at charge state +11) being linked to barium, lead, copper, and zinc in their divalent forms. Metalloprotein speciation analysis was carried out for copper (Cu(+) and Cu(2+)), lead (Pb(2+) and Pb(4+)), and selenium (Se(4+) and Se(6+)) species complexed with bovine carbonic anhydrase. Mobilities of all complexed species were compared, also considering the apo form of this protein.

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.

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

International Nuclear Information System (INIS)

Zhong Huan; Wang Wenxiong

2008-01-01

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

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

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...

Cytotoxic and phenotypic effects of uranium and lead on osteoblastic cells are highly dependent on metal speciation

International Nuclear Information System (INIS)

Milgram, S.; Carriere, M.; Thiebault, C.; Malaval, L.; Gouget, B.

2008-01-01

Bone is one of the main retention organs for uranium (U) and lead (Pb). The clinical effects of U or Pb poisoning are well known: acute and chronic intoxications impair bone formation. However, only few studies dealt with the cellular and molecular mechanisms of their toxicity. The purpose of this study was to investigate acute cytotoxicity of U and Pb and their phenotypic effects on rat and human osteoblasts, the cells responsible for bone formation. The most likely species of the toxicants in contact with cells after blood contamination were selected for cell exposure. Results showed that the cytotoxic effect of U and Pb is highly dependent on their speciation. Thus, Pb was cytotoxic when left free in the exposure medium or when complexed with carbonate, cystein or citrate, but not when complexed with albumin or phosphate, under an insoluble form. U was cytotoxic whatever its speciation, but differences in sensitivity were observed as a function of speciation. Population growth recovery could be obtained after exposure to low doses of U or Pb, except for some U-carbonate complexes which had irreversible effects whatever the dose. The activation of two markers of bone formation and mineralization, osteocalcin and bone sialoprotein (BSP), was observed after exposure to non-toxic doses or non-toxic species of U or Pb while their inhibition was observed after toxic exposure to both metals. This work provides new elements to better understand the complex mechanisms of U and Pb toxicity to osteoblasts. Our results also illustrate the importance of a strictly controlled speciation of the metals in toxicological studies

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.)

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.)

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

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.

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.

The radiolytic and chemical degradation of organic ion exchange resins under alkaline conditions: effect on radionuclide speciation

Energy Technology Data Exchange (ETDEWEB)

Loon, L. van; Hummel, W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1995-10-01

The formation of water soluble organic ligands by the radiolytic and chemical degradation of several ion exchange resins was investigated under conditions close to those of the near field of a cementitious repository. The most important degradation products were characterised and their role on radionuclide speciation evaluated thoroughly. Irradiation of strong acidic cation exchange resins (Powdex PCH and Lewatite S-100) resulted in the formation of mainly sulphate and dissolved organic carbon. A small part of the carbon (10-20%) could be identified as oxalate. The identity of the remainder is unknown. Complexation studies with Cu{sup 2+} and Ni{sup 2+} showed the presence of two ligands: oxalate and ligand X. Although ligand X could not be identified, it could be characterised by its concentration, a deprotonation constant and a complexation constant for the NiX complex. The influence of oxalate and ligand X on the speciation of radionuclides is examined in detail. For oxalate no significant influence on the speciation of radionuclides is expected. The stronger complexing ligand X may exert some influence depending on its concentration and the values of other parameters. These critical parameters are discussed and limiting values are evaluated. In absence of irradiation, no evidence for the formation of ligands was found. Irradiation of strong basic anion exchange resins (Powdex PAO and Lewatite M-500) resulted in the formation of mainly ammonia, amines and dissolved organic carbon. Up to 50% of the carbon could be identified as methyl-, dimethyl- and trimethylamine. Complexation studies with Eu{sup 3+} showed that the complexing capacity under near field conditions was negligible. The speciation of cations such as Ag, Ni, Cu and Pd can be influenced by the presence of amins. The strongest amine-complexes are formed with Pd and therefore, as an example, the aqueous Pd-ammonia system is examined in great detail. (author) 30 figs., 10 tabs., refs.

Speciation of the plutonium at trace levels by capillary electrophoresis-ICP-MS coupling

International Nuclear Information System (INIS)

Ambard, Ch.

2007-01-01

The CE-ICP-MS coupling allowed the development of new analytical methods for the study of plutonium speciation at trace levels including complexation studies of this element by organic and inorganic ligands. First, a method, called dual detection, based on the simultaneous use of the UV-Visible spectrophotometer integrated in the capillary electrophoresis and the ICPMS was developed and validated. It allows the unambiguous determination of electrophoretic mobilities for separated chemical species and gives a powerful tool for speciation studies. Then, the influence on plutonium redox speciation of the buffer from the background electrolyte was evaluated. This study showed the implications of the electrolyte constituents' choice on plutonium redox equilibrium in the sample. Furthermore, the CE-ICP-MS coupling was used for studying the plutonium complexation at trace levels by some organic (NTA and DTPA) and inorganic ligands (carbonates). The behaviour of plutonium valence +III, +IV and +VI was studied in the presence of buffer at near neutral pH. Different species of plutonium were observed depending on the initial oxidation state of the plutonium. This study showed the potential of poly-amino-carboxylic acids, such as NTA and DTPA, for dissolving plutonium precipitates, regardless its initial speciation. Finally, the carbonation of pentavalent neptunium, as an analogue of Pu(V), was achieved at very low concentration of Np (10 -8 mol.L -1 ). The formation constant of NpO 2 (CO 3 )- at 25 deg. C and 2,5 x 10 -2 mol.L -1 ionic strength was measured by CE-ICP-MS and found to be consistent with literature data. (author)

Speciation of the plutonium at trace levels by capillary electrophoresis-ICP-MS coupling

International Nuclear Information System (INIS)

Ambard, Ch.

2007-01-01

The CE-ICP-MS coupling allowed the development of new analytical methods for the study of plutonium (Pu) speciation at trace levels including complexation studies of this element by organic and inorganic ligands. First, a method, called dual detection, based on the simultaneous use of the UV-Visible spectrophotometer integrated in the capillary electrophoresis and the ICP-MS was developed and validated. It allows the unambiguous determination of electrophoretic mobilities for separated chemical species and gives a powerful tool for speciation studies. Then, the influence on Pu redox speciation of the buffer from the background electrolyte was evaluated. This study showed the implications of the electrolyte constituents' choice on Pu redox equilibrium in the sample. Furthermore, the CE-ICP-MS coupling was used for studying the Pu complexation at trace levels by some organic (NTA and DTPA) and inorganic ligands (carbonates). The behaviour of Pu valence +III, +IV and +VI was studied in the presence of buffer at near neutral pH. Different species of Pu were observed depending on the initial oxidation state of the plutonium. The study showed the potential of poly-amino-carboxylic acids, such as NTA and DTPA, for dissolving Pu precipitates, regardless its initial speciation. Finally, the carbonation of pentavalent neptunium, as an analogue of Pu(V), was achieved at very low concentration of Np (10 -8 mol.L -1 ). The formation of NpO 2 (CO 3 ) - at 25 C and 2,5*10 -2 mol.L -1 ionic strength was measured by CE-ICP-MS and found to consistent with literature data. (author)

Kinetic speciation and bioavailability of copper and nickel in mangrove sediments

Digital Repository Service at National Institute of Oceanography (India)

Chakraborty, P.; Chakraborty, S.; Ramteke, D.; Chennuri, K.

speciation (and dynamic/labile complexes) of metals in soils and sediments. The approaches include batch techniques (Beauchemin et al., 2002; Bermond and Varrault, 2004; Yu and Klarup, 1994), flow techniques (Beauchemin et al., 2002; Shiowatana et al... and mobility of metal and its migration in a polluted or naturally contaminated soils/sediments (Beauchemin et al., 2002; Bermond and Varrault, 2004; Fangueiro et al., 2002). This method is capable of determining kinetically distinguishable metal complexes...

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)

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

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...

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...

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

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)

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

Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

Science.gov (United States)

See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

2017-10-18

Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest

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...

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...

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)

Reassessing the role of sulfur geochemistry on arsenic speciation in reducing environments

KAUST Repository

Couture, Raoul-Marie

2011-05-01

Recent evidence suggests that the oxidation of arsenite by zero-valent sulfur (S(0)) may produce stable aqueous arsenate species under highly reducing conditions. The speciation of arsenic (As) in reducing soils, sediments and aquifers may therefore be far more complex than previously thought. We illustrate this by presenting updated Eh-pH diagrams of As speciation in sulfidic waters that include the most recently reported formation constants for sulfide complexes of As(III) and As(V). The results show that the stability fields of As(III) and As(V) (oxy)thioanions cover a large pH range, from pH 5 to 10. In particular, As(V)-S(-II) complexes significantly enhance the predicted solubility of As under reducing conditions. Equilibrium calculations further show that, under conditions representative of sulfidic pore waters and in the presence of solid-phase elemental sulfur, the S0 (aq)/HS- couple yields a redox potential (Eh)~0.1V higher than the SO4 2-/HS- couple. S(0) may thus help stabilize aqueous As(V) not only by providing an electron acceptor for As(III) but also by contributing to a more oxidizing redox state. © 2011 Elsevier B.V.

Reassessing the role of sulfur geochemistry on arsenic speciation in reducing environments

KAUST Repository

Couture, Raoul-Marie; Van Cappellen, Philippe

2011-01-01

Recent evidence suggests that the oxidation of arsenite by zero-valent sulfur (S(0)) may produce stable aqueous arsenate species under highly reducing conditions. The speciation of arsenic (As) in reducing soils, sediments and aquifers may therefore be far more complex than previously thought. We illustrate this by presenting updated Eh-pH diagrams of As speciation in sulfidic waters that include the most recently reported formation constants for sulfide complexes of As(III) and As(V). The results show that the stability fields of As(III) and As(V) (oxy)thioanions cover a large pH range, from pH 5 to 10. In particular, As(V)-S(-II) complexes significantly enhance the predicted solubility of As under reducing conditions. Equilibrium calculations further show that, under conditions representative of sulfidic pore waters and in the presence of solid-phase elemental sulfur, the S0 (aq)/HS- couple yields a redox potential (Eh)~0.1V higher than the SO4 2-/HS- couple. S(0) may thus help stabilize aqueous As(V) not only by providing an electron acceptor for As(III) but also by contributing to a more oxidizing redox state. © 2011 Elsevier B.V.

Inorganic speciation of dissolved elements in seawater: the influence of pH on concentration ratios

Directory of Open Access Journals (Sweden)

Byrne Robert H

2002-01-01

Full Text Available Assessments of inorganic elemental speciation in seawater span the past four decades. Experimentation, compilation and critical review of equilibrium data over the past forty years have, in particular, considerably improved our understanding of cation hydrolysis and the complexation of cations by carbonate ions in solution. Through experimental investigations and critical evaluation it is now known that more than forty elements have seawater speciation schemes that are strongly influenced by pH. In the present work, the speciation of the elements in seawater is summarized in a manner that highlights the significance of pH variations. For elements that have pH-dependent species concentration ratios, this work summarizes equilibrium data (S = 35, t = 25°C that can be used to assess regions of dominance and relative species concentrations. Concentration ratios of complex species are expressed in the form log[A]/[B] = pH - C where brackets denote species concentrations in solution, A and B are species important at higher (A and lower (B solution pH, and C is a constant dependent on salinity, temperature and pressure. In the case of equilibria involving complex oxy-anions (MOx(OHy or hydroxy complexes (M(OHn, C is written as pKn = -log Kn or pKn* = -log Kn* respectively, where Kn and Kn* are equilibrium constants. For equilibria involving carbonate complexation, the constant C is written as pQ = -log(K2lKn [HCO3-] where K2l is the HCO3 - dissociation constant, Kn is a cation complexation constant and [HCO3-] is approximated as 1.9 × 10-3 molar. Equilibrium data expressed in this manner clearly show dominant species transitions, ranges of dominance, and relative concentrations at any pH.

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.

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

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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

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.)

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

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.

Characteristics of PM2.5 speciation in representative megacities and across China

Science.gov (United States)

Yang, F.; Tan, J.; Zhao, Q.; Du, Z.; He, K.; Ma, Y.; Duan, F.; Chen, G.; Zhao, Q.

2011-06-01

Based on PM2.5 chemical data sets from literature and from our surface observations, chemical species and reconstructed speciation of PM2.5 in representative Chinese megacities and across China were compared to draw insights into the characteristics of PM2.5 speciation. PM2.5 mass concentrations and speciation compositions varied substantially over geographical regions in China. Near six-fold variations in average PM2.5 concentrations (34.0-193.4 μg m-3) across China were found with high PM2.5 levels (>100 μg m-3) appearing in the cities in the northern and western regions and low levels (transport of the secondary aerosols, thus more intensive characteristic of "complex atmospheric pollution" compared to the western region. Organic matter had significant contribution to PM2.5 over all the sites. Organic matter plus sulfate, nitrate, and ammonia accounted for 53-90 % of PM2.5 mass across China. PM2.5 speciation across China was also characterized by high content of crustal material, which was usually at more than ~10 μg m-3 level or shared ~10 % of PM2.5 mass in urban areas, due to transported desert dust and locally induced dust. In four representative megacities (i.e. Beijing, Chongqing, Shanghai, and Guangzhou), PM2.5 mass and major components (except sulfate) were at higher levels than those in US continental east by one order of magnitude. Distinct differences in nitrate and sulfate levels and their mass ratio [NO3-]/[SO42-] imply that mobile sources are likely more important in Guangzhou, whereas in Chongqing it is stationary (coal combustion) sources. The observed intra-city variations in PM2.5 mass and speciation indicate that both local emissions and regional transportation contributed significantly to high fine particle loadings in Beijing, while local contribution likely played a predominant role in Chongqing. During the ten-year period from 1999 through 2008 in urban Beijing, both the sum of sulfate, nitrate, and ammonia and [NO3-]/[SO42-] ratio

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

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)

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

Directory of Open Access Journals (Sweden)

Magdalena Jabłońska-Czapla

2015-01-01

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

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

Complex patterns of speciation in cosmopolitan "rock posy" lichens--discovering and delimiting cryptic fungal species in the lichen-forming Rhizoplaca melanophthalma species-complex (Lecanoraceae, Ascomycota).

Science.gov (United States)

Leavitt, Steven D; Fankhauser, Johnathon D; Leavitt, Dean H; Porter, Lyndon D; Johnson, Leigh A; St Clair, Larry L

2011-06-01

A growing body of evidence indicates that in some cases morphology-based species circumscription of lichenized fungi misrepresents the number of existing species. The cosmopolitan "rock posy" lichen (Rhizoplaca melanophthalma) species-complex includes a number of morphologically distinct species that are both geographically and ecologically widespread, providing a model system to evaluate speciation in lichen-forming ascomycetes. In this study, we assembled multiple lines of evidence from nuclear DNA sequence data, morphology, and biochemistry for species delimitation in the R. melanophthalma species-complex. We identify a total of ten candidate species in this study, four of which were previously recognized as distinct taxa and six previously unrecognized lineages found within what has been thus far considered a single species. Candidate species are supported using inferences from multiple empirical operational criteria. Multiple instances of sympatry support the view that these lineages merit recognition as distinct taxa. Generally, we found little corroboration between morphological and chemical characters, and previously unidentified lineages were morphologically polymorphic. However, secondary metabolite data supported one cryptic saxicolous lineage, characterized by orsellinic-derived gyrophoric and lecanoric acids, which we consider to be taxonomically significant. Our study of the R. melanophthalma species-complex indicates that the genus Rhizoplaca, as presently circumscribed, is more diverse in western North American than originally perceived, and we present our analyses as a working example of species delimitation in morphologically cryptic and recently diverged lichenized fungi. Copyright © 2011 Elsevier Inc. All rights reserved.

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

Scanning transmission X-ray microscopy as a speciation tool for natural organic molecules

Energy Technology Data Exchange (ETDEWEB)

Rothe, J.; Plaschke, M.; Denecke, M.A. [Inst. fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Karlsruhe (Germany)

2004-07-01

A molecular-scale understanding of the basic processes affecting stability and transport behavior of actinide cations, complexes or hydroxide ('eigencolloid') species is prerequisite to performance assessment of nuclear waste disposal in geological formations. Depending on their functional group chemistry and macromolecular structure, naturally occurring organic molecules (NOM) possess a high tendency towards actinide complexation reactions. However, the compositional and structural heterogeneity of NOM and mixed aggregates with inorganic phases makes speciation by spectromicroscopy techniques highly desirable. The applicability of Scanning Transmission X-ray Microscopy (STXM) as a speciation tool for the characterization of NOM is demonstrated for a multifunctional natural organic acid (chlorogenic acid), Eu(III)-loaded humic acid (HA) aggregates and Eu(III)-oxo/hydroxide/HA hetero-aggregates. It is shown that in situ probing of HA functional group chemistry down to a spatial resolution < 100 nm (i.e., less than femto-liter sampled volumes) is feasible, at the same time revealing morphological details on NOM aggregates and NOM/mineral associations. (orig.)

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

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.

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.)

Radiating on oceanic islands: patterns and processes of speciation in the land snail genus Theba (Risso 1826.

Directory of Open Access Journals (Sweden)

Carola Greve

Full Text Available Island radiations have played a major role in shaping our current understanding of allopatric, sympatric and parapatric speciation. However, the fact that species divergence correlates with island size emphasizes the importance of geographic isolation (allopatry in speciation. Based on molecular and morphological data, we investigated the diversification of the land snail genus Theba on the two Canary Islands of Lanzarote and Fuerteventura. Due to the geological history of both islands, this study system provides ideal conditions to investigate the interplay of biogeography, dispersal ability and differentiation in generating species diversity. Our analyses demonstrated extensive cryptic diversification of Theba on these islands, probably driven mainly by non-adaptive allopatric differentiation and secondary gene flow. In a few cases, we observed a complete absence of gene flow among sympatrically distributed forms suggesting an advanced stage of speciation. On the Jandía peninsula genome scans suggested genotype-environment associations and potentially adaptive diversification of two closely related Theba species to different ecological environments. We found support for the idea that genetic differentiation was enhanced by divergent selection in different environments. The diversification of Theba on both islands is therefore best explained by a mixture of non-adaptive and adaptive speciation, promoted by ecological and geomorphological factors.

Radiating on oceanic islands: patterns and processes of speciation in the land snail genus Theba (Risso 1826).

Science.gov (United States)

Greve, Carola; Gimnich, France; Hutterer, Rainer; Misof, Bernhard; Haase, Martin

2012-01-01

Island radiations have played a major role in shaping our current understanding of allopatric, sympatric and parapatric speciation. However, the fact that species divergence correlates with island size emphasizes the importance of geographic isolation (allopatry) in speciation. Based on molecular and morphological data, we investigated the diversification of the land snail genus Theba on the two Canary Islands of Lanzarote and Fuerteventura. Due to the geological history of both islands, this study system provides ideal conditions to investigate the interplay of biogeography, dispersal ability and differentiation in generating species diversity. Our analyses demonstrated extensive cryptic diversification of Theba on these islands, probably driven mainly by non-adaptive allopatric differentiation and secondary gene flow. In a few cases, we observed a complete absence of gene flow among sympatrically distributed forms suggesting an advanced stage of speciation. On the Jandía peninsula genome scans suggested genotype-environment associations and potentially adaptive diversification of two closely related Theba species to different ecological environments. We found support for the idea that genetic differentiation was enhanced by divergent selection in different environments. The diversification of Theba on both islands is therefore best explained by a mixture of non-adaptive and adaptive speciation, promoted by ecological and geomorphological factors.

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.

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.

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.

Study of the impact of environmental bacteria ob uranium speciation in order to engage bioremediation process

International Nuclear Information System (INIS)

Untereiner, G.

2008-11-01

Uranium is both a radiological and a chemical toxic. Its concentration in the environment is low except when human activities have caused pollution. Uranium is a heavy reactive element, and thus it is easily complexed with soil component like minerals or organic molecules. These different complexes can be more or less bioavailable for microorganisms and plants, and then get in the human food chain. The knowledge and the understanding of transfer mechanisms and also the fate of toxic elements in the biosphere are a key issue to estimate health and ecological hazards. The knowledge of the speciation is very important for bioremediation processes. Here, we focused on the microorganisms effects onto uranium speciation in environment. Bacteria can accumulate and/or transform uranium depending on the initial form of the element. Thus, its bioavailability could be changed. The species used in this work are Cupriavidus metallidurans CH34, which is an environmental bacteria with a high resistance to heavy metal, Deinococcus radiodurans R1, which is known for his radiological resistance, and Rhodopseudomonas palustris, which is a purple photo-trophic bacteria capable of degrading aromatic compounds. Two forms of uranium were used with these bacteria, a mineral one, uranyl carbonate, and an organic one, uranyl citrate. In a first step, the growth media were modified in order to stabilize uranium complexes thanks to a simulation program. Then, the capacity of the bacteria to accumulate or transform uranium was studied. We saw a difference between minimal inhibition concentrations of these two speciation which is due to a difference between phosphate bioavailability. No accumulation was observed with environmental pH but uranium precipitation was observed with acidic pH (pH 1). Uranium speciation seemed to be well controlled in the growth media and the precipitates were uranyl phosphate. (author)

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

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.

Trace metal characterization and speciation in geothermal effluent by multiple scanning anodic stripping voltammetry and atomic absorption analysis

Energy Technology Data Exchange (ETDEWEB)

Kowalski, B.R.

1979-05-25

Recent studies have shown geothermal power plants to have a significant environmental impact on the ground water of the area. The heavy metals arsenic and mercury are special problems, as both are concentrated by flora and fauna exposed to the effluent waters. Because the toxicity of these and other metallic pollutants present in geothermal effluent depends on the chemical form, or speciation, of the particular metal, any serious study of the environmental impact of a geothermal development should include studies of trace metal speciation, in addition to trace metal concentration. This proposal details a method for determining metal speciation in dilute waters. The method is based on ion-exchange and backed by atomic absorption spectrometry and multiple scanning anodic stripping voltammetry. Special laboratory studies will be performed on mercury, arsenic and selenium speciation in synthetic geothermal water. The method will be applied to three known geothermal areas in Washington and Oregon, with emphasis on the speciation of mercury, arsenic and selenium in these waters. The computer controlled electrochemical instrumentation was built and tested. Using this instrumentation, a new experimental procedure was developed to determine the chemical form (speciation) of metal ions in very dilute solutions (ng/ml). This method was tested on model systems including Pb, Cd, and As with C1/sup -/, CO/sub 3//sup 2 -/ and glycine ligands. Finally, the speciation of lead in a geothermal water was examined and the PbC1/sup +/ complex was observed and quantified.

Quantitative HPLC-ICP-MS analysis of antimony redox speciation in complex sample matrices: new insights into the Sb-chemistry causing poor chromatographic recoveries

DEFF Research Database (Denmark)

Hansen, Claus; Schmidt, Bjørn; Larsen, Erik Huusfeldt

2011-01-01

In solution antimony exists either in the pentavalent or trivalent oxidation state. As Sb(III) is more toxic than Sb(V), it is important to be able to perform a quantitative speciation analysis of Sb’s oxidation state. The most commonly applied chromatographic methods used for this redox speciation...

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:...

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)

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

Recurrent hybridization and recent origin obscure phylogenetic relationships within the ‘white-headed’ gull (Larus sp.) complex

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Sonsthagen, Sarah A.; Wilson, Robert E.; Chesser, Terry; Pons, Jean-Marc; Crochet, Pierre-Andre; Driscoll, Amy; Dove, Carla

2016-01-01

Species complexes that have undergone recent radiations are often characterized by extensive allele sharing due to recent ancestry and (or) introgressive hybridization. This can result in discordant evolutionary histories of genes and heterogeneous genomes, making delineating species limits difficult. Here we examine the phylogenetic relationships among a complex group of birds, the white-headed gulls (Aves: Laridae), which offer a unique window into the speciation process due to their recent evolutionary history and propensity to hybridize. Relationships were examined among 17 species (61 populations) using a multilocus approach, including mitochondrial and nuclear intron DNA sequences and microsatellite genotype information. Analyses of microsatellite and intron data resulted in some species-based groupings, although most species were not represented by a single cluster. Considerable allele and haplotype sharing among white-headed gull species was observed; no locus contained a species-specific clade. Despite this, our multilocus approach provided better resolution among some species than previous studies. Interestingly, most clades appear to correspond to geographic locality: our BEAST analysis recovered strong support for a northern European/Icelandic clade, a southern European/Russian clade, and a western North American/canus clade, with weak evidence for a high latitude clade spanning North America and northwestern Europe. This geographical structuring is concordant with behavioral observations of pervasive hybridization in areas of secondary contact. The extent of allele and haplotype sharing indicates that ecological and sexual selection are likely not strong enough to complete reproductive isolation within several species in the white-headed gull complex. This suggests that just a few genes are driving the speciation process.

The Phylogeny and Biogeographic History of Ashes (Fraxinus, Oleaceae) Highlight the Roles of Migration and Vicariance in the Diversification of Temperate Trees

Science.gov (United States)

Hinsinger, Damien Daniel; Basak, Jolly; Gaudeul, Myriam; Cruaud, Corinne; Bertolino, Paola; Frascaria-Lacoste, Nathalie; Bousquet, Jean

2013-01-01

The cosmopolitan genus Fraxinus, which comprises about 40 species of temperate trees and shrubs occupying various habitats in the Northern Hemisphere, represents a useful model to study speciation in long-lived angiosperms. We used nuclear external transcribed spacers (nETS), phantastica gene sequences, and two chloroplast loci (trnH-psbA and rpl32-trnL) in combination with previously published and newly obtained nITS sequences to produce a time-calibrated multi-locus phylogeny of the genus. We then inferred the biogeographic history and evolution of floral morphology. An early dispersal event could be inferred from North America to Asia during the Oligocene, leading to the diversification of the section Melioides sensus lato. Another intercontinental dispersal originating from the Eurasian section of Fraxinus could be dated from the Miocene and resulted in the speciation of F. nigra in North America. In addition, vicariance was inferred to account for the distribution of the other Old World species (sections Sciadanthus, Fraxinus and Ornus). Geographic speciation likely involving dispersal and vicariance could also be inferred from the phylogenetic grouping of geographically close taxa. Molecular dating suggested that the initial divergence of the taxonomical sections occurred during the middle and late Eocene and Oligocene periods, whereas diversification within sections occurred mostly during the late Oligocene and Miocene, which is consistent with the climate warming and accompanying large distributional changes observed during these periods. These various results underline the importance of dispersal and vicariance in promoting geographic speciation and diversification in Fraxinus. Similarities in life history, reproductive and demographic attributes as well as geographical distribution patterns suggest that many other temperate trees should exhibit similar speciation patterns. On the other hand, the observed parallel evolution and reversions in floral

How does male–male competition generate negative frequency-dependent selection and disruptive selection during speciation?

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Border, Shana E

2018-01-01

Abstract Natural selection has been shown to drive population differentiation and speciation. The role of sexual selection in this process is controversial; however, most of the work has centered on mate choice while the role of male–male competition in speciation is relatively understudied. Here, we outline how male–male competition can be a source of diversifying selection on male competitive phenotypes, and how this can contribute to the evolution of reproductive isolation. We highlight how negative frequency-dependent selection (advantage of rare phenotype arising from stronger male–male competition between similar male phenotypes compared with dissimilar male phenotypes) and disruptive selection (advantage of extreme phenotypes) drives the evolution of diversity in competitive traits such as weapon size, nuptial coloration, or aggressiveness. We underscore that male–male competition interacts with other life-history functions and that variable male competitive phenotypes may represent alternative adaptive options. In addition to competition for mates, aggressive interference competition for ecological resources can exert selection on competitor signals. We call for a better integration of male–male competition with ecological interference competition since both can influence the process of speciation via comparable but distinct mechanisms. Altogether, we present a more comprehensive framework for studying the role of male–male competition in speciation, and emphasize the need for better integration of insights gained from other fields studying the evolutionary, behavioral, and physiological consequences of agonistic interactions. PMID:29492042

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

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

Science.gov (United States)

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

2016-03-01

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

Impact of Eu(III) on mammalian cells as a function of its speciation

Energy Technology Data Exchange (ETDEWEB)

Sachs, Susanne; Heller, Anne; Geipel, Gerhard; Bernhard, Gert [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Bautzner Landstr. 400, 01328 Dresden (Germany)

2014-07-01

toxicity of U(VI) onto rat kidney cells [3]. In the presence of fetal bovine serum (FBS) as nutrient component, Eu(III) is stabilized in solution by complexation with serum proteins as strong complexing agents and shows a low cytotoxicity. In contrast to that, in the absence of FBS, Eu(III) forms hardly soluble species that are dominated by phosphate ligands. In this binding form, Eu(III) exerts a significantly higher cytotoxicity. The presence of an excess of citrate, as strong complexing ligand, influences the Eu(III) speciation and decreases its toxicity in the absence of FBS. Independent of its speciation, Eu(III) seems to be predominantly bound to the cell surface and does not significantly enter the cells. Under the applied experimental conditions, the tolerance of FaDu cells versus Eu(III) appears to be not significantly influenced by the presence of {sup 152}Eu, indicating no additional radio-toxic effect. (authors)

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.

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.

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...

Coordination chemistry of two heavy metals: I, Ligand preferences in lead(II) complexation, toward the development of therapeutic agents for lead poisoning: II, Plutonium solubility and speciation relevant to the environment

International Nuclear Information System (INIS)

Neu, M.P.

1993-11-01

The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK a s and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK a = 5.94, logβ 120 = 10.92; acetohydroxamic acid, pK a = 9.34, logβ l20 = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinate geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is logβ 110 = 41.7. The solubility limited speciation of 242 Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods

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.

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.

Confirmation of vanadium complex formation using electrospray mass spectrometry and determination of vanadium speciation by sample stacking capillary electrophoresis

International Nuclear Information System (INIS)

Chen Zuliang; Owens, Gary; Naidu, Ravendra

2007-01-01

Capillary zone electrophoresis (CZE) with UV detection was used to determine vanadium species. Nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) and 2,6-pyridinedicarboxylic acid (PDCA) were investigated to determine whether these ligands formed stable anionic complexes with vanadium. Of all the ligands studied HEDTA was the most suitable ligand because it gave the largest UV response with reasonable migration time. Electrospray mass spectrometry (ES-MS) was used to confirm the formation of [VO 2 (HEDTA)] 2- and [VO(HEDTA)] 1- in solution. An electrolyte containing 25 mM phosphate, 0.25 mM tetradecyltrimethylammonium bromide (TTAB) at pH 5.5 was optimum for the separation of these anionic vanadium complexes. Sample stacking techniques, including large-volume sample stacking (LVSS) and field-amplified sample injection (FASI), were tested to improve the sensitivity. Best sensitivity was obtained using FASI, with detection limits of 0.001 μM, equivalent to 0.4 μg L -1 , for [VO 2 (HEDTA)] 2- and 0.01 μM, equivalent to 3.4 μg L -1 for [VO(HEDTA)] 1- . The utility of the method for the speciation of V(IV) and V(V) was demonstrated using ground water samples

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.

Hybridization and genome evolution I: The role of contingency during hybrid speciation

Directory of Open Access Journals (Sweden)

Fabrice EROUKHMANOFF, Richard I. BAILEY, Glenn-Peter SæTRE

2013-10-01

Full Text Available Homoploid hybrid speciation (HHS involves the recombination of two differentiated genomes into a novel, functional one without a change in chromosome number. Theoretically, there are numerous ways for two parental genomes to recombine. Hence, chance may play a large role in the formation of a hybrid species. If these genome combinations can evolve rapidly following hybridization and sympatric situations are numerous, recurrent homoploid hybrid speciation is a possibility. We argue that three different, but not mutually exclusive, types of contingencies could influence this process. First, many of these “hopeful monsters” of recombinant parent genotypes would likely have low fitness. Only specific combinations of parental genomic contributions may produce viable, intra-fertile hybrid species able to accommodate potential constraints arising from intragenomic conflict. Second, ecological conditions (competition, geography of the contact zones or the initial frequency of both parent species might favor different outcomes ranging from sympatric coexistence to the formation of hybrid swarms and ultimately hybrid speciation. Finally, history may also play an important role in promoting or constraining recurrent HHS if multiple hybridization events occur sequentially and parental divergence or isolation differs along this continuum. We discuss under which conditions HHS may occur multiple times in parallel and to what extent recombination and selection may fuse the parent genomes in the same or different ways. We conclude by examining different approaches that might help to solve this intriguing evolutionary puzzle [Current Zoology 59 (5: 667-674, 2013].　

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.

Allochronic speciation, secondary contact, and reproductive character displacement in periodical cicadas (Hemiptera: Magicicada spp.): genetic, morphological, and behavioural evidence.

Science.gov (United States)

Cooley, J R; Simon, C; Marshall, D C; Slon, K; Ehrhardt, C

2001-03-01

Periodical cicadas have proven useful in testing a variety of ecological and evolutionary hypotheses because of their unusual life history, extraordinary abundance, and wide geographical range. Periodical cicadas provide the best examples of synchronous periodicity and predator satiation in the animal kingdom, and are excellent illustrations of habitat partitioning (by the three morphologically distinct species groups), incipient species (the year classes or broods), and cryptic species (a newly discovered 13-year species, Magicicada neotredecim). They are particularly useful for exploring questions regarding speciation via temporal isolation, or allochronic speciation. Recently, data were presented that provided strong support for an instance of allochronic speciation by life-cycle switching. This speciation event resulted in the formation of a new 13-year species from a 17-year species and led to secondary contact between two formerly separated lineages, one represented by the new 13-year cicadas (and their 17-year ancestors), and the other represented by the pre-existing 13-year cicadas. Allozyme frequency data, mitochondrial DNA (mtDNA), and abdominal colour were shown to be correlated genetic markers supporting the life-cycle switching/allochronic speciation hypothesis. In addition, a striking pattern of reproductive character displacement in male call pitch and female pitch preference between the two 13-year species was discovered. In this paper we report a strong association between calling song pitch and mtDNA haplotype for 101 individuals from a single locality within the M. tredecim/M. neotredecim contact zone and a strong association between abdomen colour and mtDNA haplotype. We conclude by reviewing proposed mechanisms for allochronic speciation and reproductive character displacement.

Cadmium speciation and accumulation in periphyton in a small stream with dynamic concentration variations

Energy Technology Data Exchange (ETDEWEB)

Bradac, Philippe [Eawag, Swiss Federal Institute of Aquatic Science and Technology, P.O. Box 611, CH-8600 Duebendorf (Switzerland); ETH, Swiss Federal Institute of Technology, Department of Environmental Sciences, CH-8092 Zurich (Switzerland); Wagner, Bettina; Kistler, David; Traber, Jacqueline; Behra, Renata [Eawag, Swiss Federal Institute of Aquatic Science and Technology, P.O. Box 611, CH-8600 Duebendorf (Switzerland); Sigg, Laura, E-mail: laura.sigg@eawag.c [Eawag, Swiss Federal Institute of Aquatic Science and Technology, P.O. Box 611, CH-8600 Duebendorf (Switzerland); ETH, Swiss Federal Institute of Technology, Department of Environmental Sciences, CH-8092 Zurich (Switzerland)

2010-03-15

Accumulation of cadmium in periphyton was investigated under field conditions while Cd concentration and speciation were dynamically varying in a small stream during rain events. Speciation in water was determined in situ by diffusion gradient in thin-films (DGT) and by modeling of complexation with fulvic acids. During the rain events, dissolved Cd concentrations increased from 0.17 nM to 0.27-0.36 nM, and 70-97% were DGT-labile. Cd content in periphyton closely followed Cd concentrations in water, despite higher concentrations of Zn and Mn, and may be controlled by either free or DGT-labile Cd concentrations. Decrease of Cd content in periphyton after the rain events was slower than the decrease of Cd concentration in water. Concentrations of Zn, Mn, Cu, Pb and Fe in periphyton also followed the dynamic variations of metal concentrations in water. Repeated exposure of periphyton to elevated dissolved Cd may lead to Cd accumulation. - Cadmium accumulation in periphyton was examined in a small stream during rain events in relation to Cd speciation.

Cadmium speciation and accumulation in periphyton in a small stream with dynamic concentration variations

International Nuclear Information System (INIS)

Bradac, Philippe; Wagner, Bettina; Kistler, David; Traber, Jacqueline; Behra, Renata; Sigg, Laura

2010-01-01

Accumulation of cadmium in periphyton was investigated under field conditions while Cd concentration and speciation were dynamically varying in a small stream during rain events. Speciation in water was determined in situ by diffusion gradient in thin-films (DGT) and by modeling of complexation with fulvic acids. During the rain events, dissolved Cd concentrations increased from 0.17 nM to 0.27-0.36 nM, and 70-97% were DGT-labile. Cd content in periphyton closely followed Cd concentrations in water, despite higher concentrations of Zn and Mn, and may be controlled by either free or DGT-labile Cd concentrations. Decrease of Cd content in periphyton after the rain events was slower than the decrease of Cd concentration in water. Concentrations of Zn, Mn, Cu, Pb and Fe in periphyton also followed the dynamic variations of metal concentrations in water. Repeated exposure of periphyton to elevated dissolved Cd may lead to Cd accumulation. - Cadmium accumulation in periphyton was examined in a small stream during rain events in relation to Cd speciation.

Disentangling the complex evolutionary history of the Western Palearctic blue tits (Cyanistes spp.) - phylogenomic analyses suggest radiation by multiple colonization events and subsequent isolation.

Science.gov (United States)

Stervander, Martin; Illera, Juan Carlos; Kvist, Laura; Barbosa, Pedro; Keehnen, Naomi P; Pruisscher, Peter; Bensch, Staffan; Hansson, Bengt

2015-05-01

Isolated islands and their often unique biota continue to play key roles for understanding the importance of drift, genetic variation and adaptation in the process of population differentiation and speciation. One island system that has inspired and intrigued evolutionary biologists is the blue tit complex (Cyanistes spp.) in Europe and Africa, in particular the complex evolutionary history of the multiple genetically distinct taxa of the Canary Islands. Understanding Afrocanarian colonization events is of particular importance because of recent unconventional suggestions that these island populations acted as source of the widespread population in mainland Africa. We investigated the relationship between mainland and island blue tits using a combination of Sanger sequencing at a population level (20 loci; 12 500 nucleotides) and next-generation sequencing of single population representatives (>3 200 000 nucleotides), analysed in coalescence and phylogenetic frameworks. We found (i) that Afrocanarian blue tits are monophyletic and represent four major clades, (ii) that the blue tit complex has a continental origin and that the Canary Islands were colonized three times, (iii) that all island populations have low genetic variation, indicating low long-term effective population sizes and (iv) that populations on La Palma and in Libya represent relicts of an ancestral North African population. Further, demographic reconstructions revealed (v) that the Canary Islands, conforming to traditional views, hold sink populations, which have not served as source for back colonization of the African mainland. Our study demonstrates the importance of complete taxon sampling and an extensive multimarker study design to obtain robust phylogeographical inferences. © 2015 John Wiley & Sons Ltd.

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

First insights into the evolutionary history of the Davallia repens complex

NARCIS (Netherlands)

Chen, C.-W.; Ngan, L.T.; Hidayat, A.; Evangelista, L.; Nooteboom, H.P.; Chiou, W.-L.

2014-01-01

Davallia repens and its close relatives have been identified as a species complex in this study because of the existence of continuously morphological variation. To decipher its evolutionary history, integrated methodologies were applied in this study including morphology, cytology, reproductive

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.

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)

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.)

The Robertsonian phenomenon in the house mouse: mutation, meiosis and speciation.

Science.gov (United States)

Garagna, Silvia; Page, Jesus; Fernandez-Donoso, Raul; Zuccotti, Maurizio; Searle, Jeremy B

2014-12-01

Many different chromosomal races with reduced chromosome number due to the presence of Robertsonian fusion metacentrics have been described in western Europe and northern Africa, within the distribution area of the western house mouse Mus musculus domesticus. This subspecies of house mouse has become the ideal model for studies to elucidate the processes of chromosome mutation and fixation that lead to the formation of chromosomal races and for studies on the impact of chromosome heterozygosities on reproductive isolation and speciation. In this review, we briefly describe the history of the discovery of the first and subsequent metacentric races in house mice; then, we focus on the molecular composition of the centromeric regions involved in chromosome fusion to examine the molecular characteristics that may explain the great variability of the karyotype that house mice show. The influence that metacentrics exert on the nuclear architecture of the male meiocytes and the consequences on meiotic progression are described to illustrate the impact that chromosomal heterozygosities exert on fertility of house mice-of relevance to reproductive isolation and speciation. The evolutionary significance of the Robertsonian phenomenon in the house mouse is discussed in the final section of this review.

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

Technetium Chemistry in HLW: Role of Organic Complexants

International Nuclear Information System (INIS)

Hess, Nancy J.; Blanchard, David L. Jr.; Campbell, James A.; Cho, Herman M.; Rai, Dhanpat Rai; Xia, Yuanxian; Conradson, Steven D.

2002-01-01

Technetium complexation with organic compounds in tank waste plays a significant role in the redox chemistry of Tc and the partitioning of Tc between the supernatant and sludge components in waste tanks. These processes need to be understood so that strategies to effectively remove Tc from high-level nuclear waste prior to waste immobilization can be developed and so that longterm consequences of Tc remaining in residual waste after sludge removal can be evaluated. Only limited data on the stability of Tc-organic complexes exists, and even less thermodynamic data on which to develop predictive models of Tc chemical behavior is available. To meet these challenges, we present a research program to study Tc-speciation in actual tank waste using state-of-the-art analytical organic chemistry, separations, and speciation techniques. On the basis of such studies, we will acquire thermodynamic data for the identified Tc-organic complexes over a wide range of chemical conditions in order to develop credible models to predict Tc speciation in tank waste and Tc behavior during waste pretreatment processing and in waste tank residuals

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)

Coordination chemistry of two heavy metals: I, Ligand preferences in lead(II) complexation, toward the development of therapeutic agents for lead poisoning: II, Plutonium solubility and speciation relevant to the environment

Energy Technology Data Exchange (ETDEWEB)

Neu, Mary Patricia [Univ. of California, Berkeley, CA (United States)

1993-11-01

The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK_as and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK_a = 5.94, logβ₁₂₀ = 10.92; acetohydroxamic acid, pK_a = 9.34, logβ₁₂₀ = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinate geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is logβ₁₂₀ = 41.7. The solubility limited speciation of ²⁴²Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods.

Speciation of Am(III)/Eu(III) sorbed on γ-alumina. Effect of metal ion concentration

International Nuclear Information System (INIS)

Kumar, S.; Tomar, B.S.; Godbole, S.V.

2013-01-01

The present paper describes the speciation of Am(III)/Eu(III) sorbed on γ-alumina, and its evolution with changing metal ion concentration, studied using batch sorption experiment, time resolved fluorescence spectroscopy (TRFS), extended X-ray absorption fine structure (EXAFS) and surface Complexation modeling (SCM). Though numerous studies exist in the literature on the speciation of trivalent actinides and lanthanides on alumina surface, the mechanism of sorption at high metal ion concentrations is not yet fully understood. Batch sorption experiments of Am(III) on γ-alumina under varying condition of pH (3-10), ionic strength (0.005-0.1 M NaClO 4 ) and metal ion concentration (10 -7 -10 -4 M) were performed. Higher metal ion concentration was achieved by the addition of Eu(III) considering it as an analogue of Am(III). Time resolved fluorescence spectroscopy (TRFS) study of Eu(III) sorbed on γ-alumina at the metal ion concentration of 5.0 x 10 -5 M was carried out over pH 4 to 7. TRFS showed the presence of two surface species, with distinctly different fluorescence decay life times. The shorter lifetime value and its changing pattern with pH indicate the surface species corresponding to this component to be monodentate species > AlOAm 2+ and its hydrolyzed forms. The sorbed Eu 3+ species corresponding to the longer lifetime value has 2-3 water molecules in its first coordination sphere and is multidentate in its binding on alumina surface. Extended X-ray absorption fine structure (EXAFS) measurement of Eu:γ-Al 2 O 3 sorption systems at pH 6.18 and 7.15 corroborate the existence of two surface complexes. Further it suggests the edge sharing bidentate binding of Eu on AlO 6 octahedra as the co-ordination mode of the higher lifetime component. Surface Complexation Modeling (SCM) of Am(III)/Eu(III) sorption onto γ-alumina at pH ≤7 has been carried out using these two surface species. 2-pK surface complexation modeling coupled with constant capacitance model

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].

History matching of a complex epidemiological model of human immunodeficiency virus transmission by using variance emulation.

Science.gov (United States)

Andrianakis, I; Vernon, I; McCreesh, N; McKinley, T J; Oakley, J E; Nsubuga, R N; Goldstein, M; White, R G

2017-08-01

Complex stochastic models are commonplace in epidemiology, but their utility depends on their calibration to empirical data. History matching is a (pre)calibration method that has been applied successfully to complex deterministic models. In this work, we adapt history matching to stochastic models, by emulating the variance in the model outputs, and therefore accounting for its dependence on the model's input values. The method proposed is applied to a real complex epidemiological model of human immunodeficiency virus in Uganda with 22 inputs and 18 outputs, and is found to increase the efficiency of history matching, requiring 70% of the time and 43% fewer simulator evaluations compared with a previous variant of the method. The insight gained into the structure of the human immunodeficiency virus model, and the constraints placed on it, are then discussed.

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

Confirmation of vanadium complex formation using electrospray mass spectrometry and determination of vanadium speciation by sample stacking capillary electrophoresis

Energy Technology Data Exchange (ETDEWEB)

Chen Zuliang [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia)]. E-mail: zuliang.chen@unisa.edu.au; Owens, Gary [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); Naidu, Ravendra [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); CRC for Contamination Assessment and Remediation of Environments, Mawson Lakes Boulevard, Mawson Lakes, SA 5095 (Australia)

2007-02-28

Capillary zone electrophoresis (CZE) with UV detection was used to determine vanadium species. Nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) and 2,6-pyridinedicarboxylic acid (PDCA) were investigated to determine whether these ligands formed stable anionic complexes with vanadium. Of all the ligands studied HEDTA was the most suitable ligand because it gave the largest UV response with reasonable migration time. Electrospray mass spectrometry (ES-MS) was used to confirm the formation of [VO{sub 2}(HEDTA)]{sup 2-} and [VO(HEDTA)]{sup 1-} in solution. An electrolyte containing 25 mM phosphate, 0.25 mM tetradecyltrimethylammonium bromide (TTAB) at pH 5.5 was optimum for the separation of these anionic vanadium complexes. Sample stacking techniques, including large-volume sample stacking (LVSS) and field-amplified sample injection (FASI), were tested to improve the sensitivity. Best sensitivity was obtained using FASI, with detection limits of 0.001 {mu}M, equivalent to 0.4 {mu}g L{sup -1}, for [VO{sub 2}(HEDTA)]{sup 2-} and 0.01 {mu}M, equivalent to 3.4 {mu}g L{sup -1} for [VO(HEDTA)]{sup 1-}. The utility of the method for the speciation of V(IV) and V(V) was demonstrated using ground water samples.

Early days in complex dynamics a history of complex dynamics in one variable during 1906-1942

CERN Document Server

Alexander, Daniel S; Rosa, Alessandro

2011-01-01

The theory of complex dynamics, whose roots lie in 19th-century studies of the iteration of complex function conducted by Kœnigs, Schröder, and others, flourished remarkably during the first half of the 20th century, when many of the central ideas and techniques of the subject developed. This book by Alexander, Iavernaro, and Rosa paints a robust picture of the field of complex dynamics between 1906 and 1942 through detailed discussions of the work of Fatou, Julia, Siegel, and several others. A recurrent theme of the authors' treatment is the center problem in complex dynamics. They present its complete history during this period and, in so doing, bring out analogies between complex dynamics and the study of differential equations, in particular, the problem of stability in Hamiltonian systems. Among these analogies are the use of iteration and problems involving small divisors which the authors examine in the work of Poincaré and others, linking them to complex dynamics, principally via the work of Samuel...

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.

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.

Radioactive contaminants in the subsurface: the influence of complexing ligands on trace metal speciation

International Nuclear Information System (INIS)

Hummel, W. . Author

2006-01-01

Equilibrium thermodynamics is one of the pillars which support safety analyzes of repositories for radioactive waste. The research summarized in this review deals with approaches to resolve the problems related to thermodynamic equilibrium constants and solubility of solid phases in the field of radioactive waste management. The results have been obtained at the Paul Scherrer Institut between 1995 and 2005 and comprise the scientific basis of the author's habilitation thesis in the field of nuclear environmental chemistry. The topics are grouped according to three different levels of problem solving strategies: critical and comprehensive reviews of the available literature, which are necessary in order to establish a reliable chemical thermodynamic database that fulfils the requirements for rigorous modeling of the behavior of the actinides and fission products in the environment. In many case studies involving inorganic and simple organic ligands a serious lack of reliable thermodynamic data is encountered. There, a new modeling approach to estimate the effects of these missing data was applied. This so called 'backdoor approach' begins with the question, 'What total concentration of a ligand is necessary to significantly influence the speciation, and hence the solubility, of a given trace metal?' In the field of natural organics, mainly humic and fulvic acids, we face an ill-defined problem concerning the molecular structure of the ligands. There, a pragmatic approach for performance assessment purposes was applied, the 'conservative roof' approach, which does not aim to accurately model all experimental data, but allows estimates of maximum effects on metal complexation by humic substances to be calculated. (author)

Origin and speciation of Picea schrenkiana and Picea smithiana in the Center Asian Highlands and Himalayas

OpenAIRE

Li, Lili; Sun, Yongshuai; Zou, Jiabin; Yue, Wei; Wang, Xi; Liu, Jianquan

2014-01-01

Elucidating the evolutionary history of current species diversity, especially trees with large effective population sizes and long generation times, is a complicated exercise confounded by gene flow and incomplete lineage sorting. In the present study, we aim to determine the origin and speciation of Picea schrenkiana and Picea smithiana using population genetic data from chloroplast (cp), mitochondrial (mt), and nuclear (nr) genomes. These two species occur in the Central Asian Highlands and...

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…

Speciation analysis of aluminium in plant parts of Betula pendula and in soil.

Science.gov (United States)

Zioła-Frankowska, Anetta; Frankowski, Marcin

2018-03-01

The research presents the first results of aluminium speciation analysis in aqueous extracts of individual plant parts of Betula pendula and soil samples, using High Performance Ion Chromatography with Diode Array Detection (HPIC-DAD). The applied method allowed us to carry out a full speciation analysis of aluminium in the form of predominant aluminium-fluoride complexes: AlF (x=2,3,4) (3-x) (first analytical signal), AlF 2+ (second analytical signal) and Al 3+ (third analytical signal) in samples of lateral roots, tap roots, twigs, stem, leaf and soil collected under roots of B. pendula. Concentrations of aluminium and its complexes were determined for two types of environment characterised by different degree of human impact: contaminated site of the Chemical Plant in Luboń and protected area of the Wielkopolski National Park. For all the analysed samples of B. pendula and soil, AlF (x=2,3,4) (3-x) had the largest contribution, followed by Al 3+ and AlF 2+ . Significant differences in concentration and contribution of Al-F complexes and Al 3+ form, depending on the place of sampling (different anthropogenic pressure) and plant part of B. pendula were observed. Based on the obtained results, it was found that transport of aluminium is "blocked" by lateral roots, and is closely related to Al content of soil. Copyright © 2017. Published by Elsevier B.V.

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)

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

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.

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)

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)

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.

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)

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

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

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

Science.gov (United States)

Koschinsky, A.; Hein, J.R.

2003-01-01

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

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

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...

Tc Chemistry in HLW: Role of Organic Complexants

International Nuclear Information System (INIS)

Hess, Nancy S.; Conradsen, Steven D.

2003-01-01

Tc complexation with organic compounds in tank waste plays a significant role in the redox chemistry of Tc and the partitioning of Tc between the supernatant and sludge components in waste tanks. These processes need to be understood so that strategies to effectively remove Tc from high-level nuclear waste prior to waste immobilization can be developed and so that long-term consequences of Tc remaining in residual waste after sludge removal can be evaluated. Only limited data on the stability of Tc-organic complexes exists and even less thermodynamic data on which to develop predictive models of Tc chemical behavior is available. To meet these challenges we are conducting a research program to study to develop thermodynamic data on Tc-organic complexation over a wide range of chemical conditions. We will attempt to characterize Tc-speciation in actual tank waste using state-of-the-art analytical organic chemistry, separations, and speciation techniques to validate our model. On the basis of such studies we will develop credible model of Tc chemistry in HLW that will allow prediction of Tc speciation in tank waste and Tc behavior during waste pretreatment processing and in waste tank residuals

Philosophy, history and sociology of science: interdisciplinary relations and complex social identities.

Science.gov (United States)

Riesch, Hauke

2014-12-01

Sociology and philosophy of science have an uneasy relationship, while the marriage of history and philosophy of science has--on the surface at least--been more successful I will take a sociological look at the history of the relationships between philosophy and history as well as philosophy and sociology of science. Interdisciplinary relations between these disciplines will be analysed through social identity complexity theory in oider to draw out some conclusions on how the disciplines interact and how they might develop. I will use the relationships between the disciplines as a pointer for a more general social theory of interdisciplinarity which will then be used to sound a caution on how interdisciplinary relations between the three disciplines might be managed.

The endemic gastropod fauna of Lake Titicaca: correlation between molecular evolution and hydrographic history.

Science.gov (United States)

Kroll, Oliver; Hershler, Robert; Albrecht, Christian; Terrazas, Edmundo M; Apaza, Roberto; Fuentealba, Carmen; Wolff, Christian; Wilke, Thomas

2012-07-01

Lake Titicaca, situated in the Altiplano high plateau, is the only ancient lake in South America. This 2- to 3-My-old (where My is million years) water body has had a complex history that included at least five major hydrological phases during the Pleistocene. It is generally assumed that these physical events helped shape the evolutionary history of the lake's biota. Herein, we study an endemic species assemblage in Lake Titicaca, composed of members of the microgastropod genus Heleobia, to determine whether the lake has functioned as a reservoir of relic species or the site of local diversification, to evaluate congruence of the regional paleohydrology and the evolutionary history of this assemblage, and to assess whether the geographic distributions of endemic lineages are hierarchical. Our phylogenetic analyses indicate that the Titicaca/Altiplano Heleobia fauna (together with few extralimital taxa) forms a species flock. A molecular clock analysis suggests that the most recent common ancestor (MRCAs) of the Altiplano taxa evolved 0.53 (0.28-0.80) My ago and the MRCAs of the Altiplano taxa and their extralimital sister group 0.92 (0.46-1.52) My ago. The endemic species of Lake Titicaca are younger than the lake itself, implying primarily intralacustrine speciation. Moreover, the timing of evolutionary branching events and the ages of two precursors of Lake Titicaca, lakes Cabana and Ballivián, is congruent. Although Lake Titicaca appears to have been the principal site of speciation for the regional Heleobia fauna, the contemporary spatial patterns of endemism have been masked by immigration and/or emigration events of local riverine taxa, which we attribute to the unstable hydrographic history of the Altiplano. Thus, a hierarchical distribution of endemism is not evident, but instead there is a single genetic break between two regional clades. We also discuss our findings in relation to studies of other regional biota and suggest that salinity tolerance was

The scale of divergence: a phylogenetic appraisal of intercontinental allopatric speciation in a passively dispersed freshwater zooplankton genus.

Science.gov (United States)

Adamowicz, Sarah J; Petrusek, Adam; Colbourne, John K; Hebert, Paul D N; Witt, Jonathan D S

2009-03-01

Molecular studies have enlightened our understanding of freshwater zooplankton biogeography, yet questions remain regarding the scale and commonality of geographic speciation. Here, we present a mtDNA-based phylogenetic hypothesis for 92 Daphnia species from all seven continents, with a focus on North and South America, Europe, and Australia, and use it to explore the frequency, scale, and geographical orientation of allopatric divergence events. Allopatric speciation can conservatively account for at least 42% of cladogenetic events among the species included in our study; most of these involve intercontinental splits. Closely related species pairs are concentrated in the circumarctic region and between northern and southern continents, aligned with bird migration routes, suggesting recent dispersal. By contrast, deeper phylogenetic patterns are consistent with vicariance scenarios linked to continental fragmentation. The possible reasons for the puzzling persistence of these ancient patterns in light of the eroding force of dispersal are considered. Our results demonstrate the high frequency and complex pattern of allopatric speciation in this ancient, passively dispersed genus.

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

Science.gov (United States)

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

2017-08-30

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

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

A climate for speciation: rapid spatial diversification within the Sorex cinereus complex of shrews

Science.gov (United States)

Hope, Andrew G.; Speer, Kelly A.; Demboski, John R.; Talbot, Sandra L.; Cook, Joseph A.

2012-01-01

The cyclic climate regime of the late Quaternary caused dramatic environmental change at high latitudes. Although these events may have been brief in periodicity from an evolutionary standpoint, multiple episodes of allopatry and divergence have been implicated in rapid radiations of a number of organisms. Shrews of the Sorex cinereus complex have long challenged taxonomists due to similar morphology and parapatric geographic ranges. Here, multi-locus phylogenetic and demographic assessments using a coalescent framework were combined to investigate spatiotemporal evolution of 13 nominal species with a widespread distribution throughout North America and across Beringia into Siberia. For these species, we first test a hypothesis of recent differentiation in response to Pleistocene climate versus more ancient divergence that would coincide with pre-Pleistocene perturbations. We then investigate the processes driving diversification over multiple continents. Our genetic analyses highlight novel diversity within these morphologically conserved mammals and clarify relationships between geographic distribution and evolutionary history. Demography within and among species indicates both regional stability and rapid expansion. Ancestral ecological differentiation coincident with early cladogenesis within the complex enabled alternating and repeated episodes of allopatry and expansion where successive glacial and interglacial phases each promoted divergence. The Sorex cinereus complex constitutes a valuable model for future comparative assessments of evolution in response to cyclic environmental change.

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

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

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.

A modelling exercise on the importance of ternary alkaline earth carbonate species of uranium(VI) in the inorganic speciation of natural waters

International Nuclear Information System (INIS)

Vercouter, Thomas; Reiller, Pascal E.; Ansoborlo, Eric; Février, Laureline; Gilbin, Rodolphe; Lomenech, Claire; Philippini, Violaine

2015-01-01

Highlights: • The U(VI) speciation in natural waters has been modelled through a modelling exercise. • The results evidence the importance of alkaline earth U(VI) carbonate complexes. • Possible solubility-controlling phases were reported and discussed. • The differences were related to the choice and reliability of thermodynamic data. • Databases need to be improved for reliable U(VI) speciation calculations. - Abstract: Predictive modelling of uranium speciation in natural waters can be achieved using equilibrium thermodynamic data and adequate speciation software. The reliability of such calculations is highly dependent on the equilibrium reactions that are considered as entry data, and the values chosen for the equilibrium constants. The working group “Speciation” of the CETAMA (Analytical methods establishment committee of the French Atomic Energy commission, CEA) has organized a modelling exercise, including four participants, in order to compare modellers’ selections of data and test thermodynamic data bases regarding the calculation of U(VI) inorganic speciation. Six different compositions of model waters were chosen so that to check the importance of ternary alkaline earth carbonate species of U(VI) on the aqueous speciation, and the possible uranium solid phases as solubility-limiting phases. The comparison of the results from the participants suggests (i) that it would be highly valuable for end-users to review thermodynamic constants of ternary carbonate species of U(VI) in a consistent way and implement them in available speciation data bases, and (ii) stresses the necessary care when using data bases to avoid biases and possible erroneous calculations

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

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...

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...

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.

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

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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.

Great genetic differentiation among populations of Meconopsis integrifolia and its implication for plant speciation in the Qinghai-Tibetan Plateau.

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Fu-Sheng Yang

Full Text Available The complex tectonic events and climatic oscillations in the Qinghai-Tibetan Plateau (QTP, the largest and highest plateau in the world, are thought to have had great effects on the evolutionary history of the native plants. Of great interest is to investigate plant population genetic divergence in the QTP and its correlation with the geologic and climatic changes. We conducted a range-wide phylogeographical analysis of M. integrifolia based on the chloroplast DNA (cpDNA trnL-trnF and trnfM-trnS regions, and defined 26 haplotypes that were phylogenetically divided into six clades dated to the late Tertiary. The six clades correspond, respectively, to highly differentiated population groups that do not overlap in geographic distribution, implying that the mountain ranges acting as corridors or barriers greatly affected the evolutionary history of the QTP plants. The older clade of M. integrifolia only occurs in the southwest of the species' range, whereas the distributions of younger clades extend northeastward in the eastern QTP, suggesting that climatic divergence resulting from the uplift of the QTP triggered the initial divergence of M. integrifolia native to the plateau. Also, the nrDNA ITS region was used to clarify the unexpected phylogenetic relationships of cpDNA haplotypes between M. integrifolia and M. betonicifolia. The topological incongruence between the two phylogenies suggests an ancestral hybridization between the two species. Our study indicates that geographic isolation and hybridization are two important mechanisms responsible for the population differentiation and speciation of Meconopsis, a species-rich genus with complex polyploids.

Laser-induced spectrometric techniques to investigate the speciation of Eu in organic media

International Nuclear Information System (INIS)

Couston, L.; Roudil, D.; Charbonnel, M.Ch.; Delage, J.; Flandin, J.L.; Mesmin, C.; Rivasseau, C.

2000-01-01

Laser-induced spectrometric techniques provide both selectivity and sensitivity. The extremely low detection limits are ideal for assessing the extraction mechanisms involved in enhanced reprocessing applications through detailed speciation studies. Although time-resolved laser-induced fluorescence spectroscopy (TRLIF) is one of the most sensitive spectroscopy techniques, with the optical spectrum and its lifetime constituting two sources of data, it is limited to a few fluorescing actinides and lanthanides. This drawback warrants the development of an additional, complementary spectroscopic system with greater sensitivity than UV-Visible-near IR absorptiometry, based on measuring the pressure wave caused by the deexcitation of non-fluorescing species. Laser-induced photoacoustic spectroscopy (LIPAS) is based on measuring the characteristics of the pressure wave emitted during non-radiative relaxation of the absorbed energy. This speciation technique should allow investigation of compounds that absorb in the UV-visible range and are present at low concentrations in solution. It provides data on the nature and concentration of the species, including its oxidation, complexation and even colloidal states. The two techniques with a common laser source OPO were recently installed at Marcoule. TRLIF speciation studies are generally based on analyzing modifications in the fluorescence spectrum following a short laser pulse. They are related to the characteristic spectral pattern and relaxation rate of each species in solution. In the particular case of fluorescent decay of trivalent Am, Cm, Sm, Eu, Tb and Dy ions, the metallic cation deexcitation constant is closely related to the number of water molecules in the primary coordination sphere. This property helps to obtain more information on the structure around the metal ion. The first study was an investigation of the complexation of Eu(III) by TEMA (N, N'-tetra-ethyl-malonamide (C 2 H 5 ) 2 NCO-CH 2 CON(C 2 H 5 ) 2 ) in

Complexation of lead by organic matter in Luanda Bay, Angola.

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Leitão, Anabela; Santos, Ana Maria; Boaventura, Rui A R

2015-10-01

Speciation is defined as the distribution of an element among different chemical species. Although the relation between speciation and bioavailability is complex, the metal present as free hydrated ion, or as weak complexes able to dissociate, is usually more bioavailable than the metal incorporated in strong complexes or adsorbed on colloidal or particulate matter. Among the analytical techniques currently available, anodic stripping voltammetry (ASV) has been one of the most used in the identification and quantification of several heavy metal species in aquatic systems. This work concerns the speciation study of lead, in original (natural, non-filtered) and filtered water samples and in suspensions of particulate matter and sediments from Luanda Bay (Angola). Complexes of lead with organics were identified and quantified by differential pulse anodic stripping voltammetry technique. Each sample was progressively titrated with a Pb(II) standard solution until complete saturation of the organic ligands. After each addition of Pb(II), the intensity, potential and peak width of the voltammetric signal were measured. The results obtained in this work show that more than 95 % of the lead in the aquatic environment is bound in inert organic complexes, considering all samples from different sampling sites. In sediment samples, the lead is totally (100 %) complexed with ligands adsorbed on the particles surface. Two kinds of dominant lead complexes, very strong (logK >11) and strong to moderately strong (8< logK <11), were found, revealing the lead affinity for the stronger ligands.

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)

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite.

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Voegelin, Andreas; Jacquat, Olivier; Pfister, Sabina; Barmettler, Kurt; Scheinost, Andreas C; Kretzschmar, Ruben

2011-01-01

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn

Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass.

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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.

Selective loss of polymorphic mating types is associated with rapid phenotypic evolution during morphic speciation.

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Corl, Ammon; Davis, Alison R; Kuchta, Shawn R; Sinervo, Barry

2010-03-02

Polymorphism may play an important role in speciation because new species could originate from the distinctive morphs observed in polymorphic populations. However, much remains to be understood about the process by which morphs found new species. To detail the steps of this mode of speciation, we studied the geographic variation and evolutionary history of a throat color polymorphism that distinguishes the "rock-paper-scissors" mating strategies of the side-blotched lizard, Uta stansburiana. We found that the polymorphism is geographically widespread and has been maintained for millions of years. However, there are many populations with reduced numbers of throat color morphs. Phylogenetic reconstruction showed that the polymorphism is ancestral, but it has been independently lost eight times, often giving rise to morphologically distinct subspecies/species. Changes to the polymorphism likely involved selection because the allele for one particular male strategy, the "sneaker" morph, has been lost in all cases. Polymorphism loss was associated with accelerated evolution of male size, female size, and sexual dimorphism, which suggests that polymorphism loss can promote rapid divergence among populations and aid species formation.

Patterns of plant speciation in the Cape floristic region.

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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.

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

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

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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.

Arsenic speciation and sorption in natural environments

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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.

Evidence for homoploid speciation in Phytophthora alni supports taxonomic reclassification in this species complex.

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Husson, C; Aguayo, J; Revellin, C; Frey, P; Ioos, R; Marçais, B

2015-04-01

Alder decline has been a problem along European watercourses since the early 1990s. Hybridization was identified as the main cause of this emerging disease. Indeed, the causal agent, a soil-borne pathogen named Phytophthora alni subsp. alni (Paa) is the result of interspecific hybridization between two taxa, Phytophthora alni subsp. multiformis (Pam) and Phytophthora alni subsp. uniformis (Pau), initially identified as subspecies of Paa. The aim of this work was to characterize the ploidy level within the P. alni complex that is presently poorly understood. For that, we used two complementary approaches for a set of 31 isolates of Paa, Pam and Pau: (i) quantification of allele copy number of three single-copy nuclear genes using allele-specific real-time PCR and (ii) comparison of the genome size estimated by flow cytometry. Relative quantification of alleles of the three single-copy genes showed that the copy number of a given allele in Paa was systematically half that of its parents Pau or Pam. Moreover, DNA content estimated by flow cytometry in Paa was equal to half the sum of those in Pam and Pau. Our results therefore suggest that the hybrid Paa is an allotriploid species, containing half of the genome of each of its parents Pam and Pau, which in turn are considered to be allotetraploid and diploid, respectively. Paa thus results from a homoploid speciation process. Based on published data and on results from this study, a new formal taxonomic name is proposed for the three taxa Paa, Pam and Pau which are raised to species status and renamed P. ×alni, P. ×multiformis and P. uniformis, respectively. Copyright © 2015 Elsevier Inc. All rights reserved.

Chemical speciation of Pb(II, Cd(II, Hg(II, Co(II, Ni(II, Cu(II and Zn(II binary complexes of l-methionine in 1,2-propanediol-water mixtures

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M. Padma Latha

2007-04-01

Full Text Available Chemical speciation of Pb(II, Cd(II, Hg(II, Co(II, Ni(II, Cu(II and Zn(II complexes of L-methionine in 0.0-60 % v/v 1,2-propanediol-water mixtures maintaining an ionic strength of 0.16 M at 303 K has been studied pH metrically. The active forms of ligand are LH2+, LH and L-. The predominant species detected are ML, MLH, ML2, ML2H, ML2H2 and MLOH. Models containing different numbers of species were refined by using the computer program MINIQUAD 75. The best-fit chemical models were arrived at based on statistical parameters. The trend in variation of complex stability constants with change in the dielectric constant of the medium is explained on the basis of electrostatic and non-electrostatic forces.

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)

The genetics of speciation by reinforcement.

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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.

First passage time to allopatric speciation.

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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.

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

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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

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.

Uranium speciation in the environment: study of opals from Nopal I (Mexico) and mill tailings from Gunnar (Canada)

International Nuclear Information System (INIS)

Othmane, G.

2012-01-01

Understanding the processes of uranium migration and sequestration is an important issue for the prediction of radionuclide retardation in the vicinity of uranium mine tailings sites or for the safety assessment of potential high-level nuclear waste repositories. Uranium speciation, controlled by biotic and abiotic factors, represents a key parameter for the control of uranium transfer in the environment. This study firstly deals with uranium speciation in opals from the Nopal I uranium deposit (Mexico). Microscopic observations of opals at the nano-scale revealed the occurrence of vorlanite, cubic CaUO 4 . This was the first time this rare calcium uranate has been found displaying a cubic morphology, in agreement with its crystal structure. Nopal I opals have been further investigated through time-resolved laser fluorescence spectroscopy. The opals spectra and their comparison with those of experimentally produced standards indicate occurrence of mono- or polymeric uranyl complexes (associated or not with calcium or phosphate) sorbed onto internal surface of opal around pH 7-8. Finally, the speciation of uranium was studied in mill tailings from Gunnar (Canada). In the first tailings site, uranium primarily occurs as monomeric, inner-sphere uranyl complexes sharing edges with Fe(O,OH) 6 octahedral sites of iron-oxy-hydroxides and chlorite. Our results suggested that U(VI) co-precipitates with iron (oxy-hydr)oxides predominate in the second tailings sites. Therefore uranium mobility in Gunnar is governed by sorption/desorption and dissolution/(co)precipitation processes. (author)

Genetic structure and bio-climatic modeling support allopatric over parapatric speciation along a latitudinal gradient.

Science.gov (United States)

Rossetto, Maurizio; Allen, Chris B; Thurlby, Katie A G; Weston, Peter H; Milner, Melita L

2012-08-20

corresponding to the four recognised species with the additional division of T. speciosissima into populations north and south of the Shoalhaven River valley. Unexpectedly, the northern disjunct population of T. oreades grouped with T. mongaensis and was identified as a hybrid swarm by the Bayesian assignment test implemented in NewHybrids. Present day and LGM environmental niche models differed dramatically, suggesting that distributions of all species had repeatedly expanded and contracted in response to Pleistocene climatic oscillations and confirming strongly marked historical distributional gaps among taxes. Genetic structure and bio-climatic modeling results are more consistent with a history of allopatric speciation followed by repeated episodes of secondary contact and localised hybridisation, rather than with parapatric speciation. This study on Telopea shows that the evidence for temporal exclusion of gene flow can be found even outside obvious geographical contexts, and that it is possible to make significant progress towards excluding parapatric speciation as a contributing evolutionary process.

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)

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

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

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

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.

Study of Coregonus Populations in the Zone of Intergradation between the Vendace and Least Cisco: the Role of the Environment in Speciation

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Borovikova Elena

2012-12-01

Full Text Available Phylogenetic analysis using mitochondrial and nuclear DNA markers showed that the Least Cisco gradually spread from Siberia to Europe until the last glaciation. This was accompanied by gradual replacement of "typically Siberian" gene variants with "typically European" ones. Morphological traits also changed as the species expanded, the changes in the body proportions being apparently adaptive. They are likely to reflect the transition of the cisco from the semi-anadromous life history type to the lacustrine type, which is more characteristic of the European form. Thus, the speciation of the vendace is clearly adaptive, at least with respect to some traits. It should be noted, however, that the results of this study raise doubt as to whether the vendace has entirely diverged from the Least Cisco, and the speciation has completed.

Inferring the demographic history of European Ficedula flycatcher populations

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Backström Niclas

2013-01-01

Full Text Available Abstract Background Inference of population and species histories and population stratification using genetic data is important for discriminating between different speciation scenarios and for correct interpretation of genome scans for signs of adaptive evolution and trait association. Here we use data from 24 intronic loci re-sequenced in population samples of two closely related species, the pied flycatcher and the collared flycatcher. Results We applied Isolation-Migration models, assignment analyses and estimated the genetic differentiation and diversity between species and between populations within species. The data indicate a divergence time between the species of Conclusions Our results provide further evidence for a divergence process where different genomic regions may be at different stages of speciation. We also conclude that forthcoming analyses of genotype-phenotype relations in these ecological model species should be designed to take population stratification into account.

Geological and anthropogenic factors influencing mercury speciation in mine wastes: An EXAFS spectroscopy study

Science.gov (United States)

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

2004-01-01

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and process, identified the presence of Hg-sulfides and schuetteite (Hg3O2SO4), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments. ?? 2003 Elsevier Ltd. All rights reserved.

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.)

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

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...

Trace elements record complex histories in diogenites

Science.gov (United States)

Balta, J. B.; Beck, A. W.; McSween, H. Y.

2012-12-01

Diogenite meteorites are cumulate rocks composed mostly of orthopyroxene and chemically linked to eucrites (basaltic) and howardites (brecciated mixtures of diogenites and eucrites). Together, they represent the largest single family of achondrite meteorites delivered to Earth, and have been spectrally linked to the asteroid 4 Vesta, the largest remaining basaltic protoplanet. However, this spectral link is non-unique as many basaltic asteroids likely formed and were destroyed in the early solar system. Recent work suggested that Vesta may be an unlikely parent body for the diogenites based on correlations between trace elements and short-lived isotope decay products, which would be unlikely to survive on a body as large as Vesta due to its long cooling history [1]. Recent analyses of terrestrial and martian olivines have demonstrated that trace element spatial distributions can preserve evidence of their crystallization history even when major elements have been homogenized [2]. We have mapped minor elements including Cr, Al, and Ti in seemingly homogeneous diogenite orthopyroxenes and found a variety of previously unobserved textures. The pyroxenes in one sample (GRA 98108) are seemingly large grains of variable shapes and sizes, but the trace elements reveal internal grain boundaries between roughly-equal sized original subgrains, with equilibrated metamorphic triple junctions between them and trace element depletions at the boundaries. These trends suggest extraction of trace elements by a magma along those relict grain boundaries during a reheating event. Two other samples show evidence of fracturing and annealing, with trace element mobility within grains. One sample appears to have remained a closed system during annealing (MET 01084), while the other has interacted with a fluid or magma to move elements along annealed cracks (LEW 88679). These relict features establish that the history of diogenite pyroxenes is more complex than their homogeneous major

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.)

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....

Sequential cloud point extraction for the speciation of mercury in seafood by inductively coupled plasma optical emission spectrometry

Energy Technology Data Exchange (ETDEWEB)

Li Yingjie [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Hu Bin [Department of Chemistry, Wuhan University, Wuhan 430072 (China)], E-mail: binhu@whu.edu.cn

2007-10-15

A novel nonchromatographic speciation technique for the speciation of mercury by sequential cloud point extraction (CPE) combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed. The method based on Hg{sup 2+} was complexed with I{sup -} to form HgI{sub 4}{sup 2-}, and the HgI{sub 4}{sup 2-} reacted with the methyl green (MG) cation to form hydrophobic ion-associated complex, and the ion-associated complex was then extracted into the surfactant-rich phase of the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114), which are subsequently separated from methylmercury (MeHg{sup +}) in the initial solution by centrifugation. The surfactant-rich phase containing Hg(II) was diluted with 0.5 mol L{sup -1} HNO{sub 3} for ICP-OES determination. The supernatant is also subjected to the similar CPE procedure for the preconcentration of MeHg{sup +} by the addition of a chelating agent, ammonium pyrrolidine dithiocarbamate (APDC), in order to form water-insolvable complex with MeHg{sup +}. The MeHg{sup +} in the micelles was directly analyzed after disposal as describe above. Under the optimized conditions, the extraction efficiency was 93.5% for Hg(II) and 51.5% for MeHg{sup +} with the enrichment factor of 18.7 for Hg(II) and 10.3 for MeHg{sup +}, respectively. The limits of detection (LODs) were 56.3 ng L{sup -1} for Hg(II) and 94.6 ng L{sup -1} for MeHg{sup +} (as Hg) with the relative standard deviations (RSDs) of 3.6% for Hg(II) and 4.5% for MeHg{sup +} (C = 10 {mu}g L{sup -1}, n = 7), respectively. The developed technique was applied to the speciation of mercury in real seafood samples and the recoveries for spiked samples were found to be in the range of 93.2-108.7%. For validation, a certified reference material of DORM-2 (dogfish muscle) was analyzed and the determined values are in good agreement with the certified values.

Sequential cloud point extraction for the speciation of mercury in seafood by inductively coupled plasma optical emission spectrometry

International Nuclear Information System (INIS)

Li Yingjie; Hu Bin

2007-01-01

A novel nonchromatographic speciation technique for the speciation of mercury by sequential cloud point extraction (CPE) combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed. The method based on Hg 2+ was complexed with I - to form HgI 4 2- , and the HgI 4 2- reacted with the methyl green (MG) cation to form hydrophobic ion-associated complex, and the ion-associated complex was then extracted into the surfactant-rich phase of the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114), which are subsequently separated from methylmercury (MeHg + ) in the initial solution by centrifugation. The surfactant-rich phase containing Hg(II) was diluted with 0.5 mol L -1 HNO 3 for ICP-OES determination. The supernatant is also subjected to the similar CPE procedure for the preconcentration of MeHg + by the addition of a chelating agent, ammonium pyrrolidine dithiocarbamate (APDC), in order to form water-insolvable complex with MeHg + . The MeHg + in the micelles was directly analyzed after disposal as describe above. Under the optimized conditions, the extraction efficiency was 93.5% for Hg(II) and 51.5% for MeHg + with the enrichment factor of 18.7 for Hg(II) and 10.3 for MeHg + , respectively. The limits of detection (LODs) were 56.3 ng L -1 for Hg(II) and 94.6 ng L -1 for MeHg + (as Hg) with the relative standard deviations (RSDs) of 3.6% for Hg(II) and 4.5% for MeHg + (C = 10 μg L -1 , n = 7), respectively. The developed technique was applied to the speciation of mercury in real seafood samples and the recoveries for spiked samples were found to be in the range of 93.2-108.7%. For validation, a certified reference material of DORM-2 (dogfish muscle) was analyzed and the determined values are in good agreement with the certified values

Along the speciation continuum: Quantifying intrinsic and extrinsic isolating barriers across five million years of evolutionary divergence in California jewelflowers.

Science.gov (United States)

Christie, Kyle; Strauss, Sharon Y

2018-05-01

Understanding the relative roles of intrinsic and extrinsic reproductive barriers, and their interplay within the geographic context of diverging taxa, remains an outstanding challenge in the study of speciation. We conducted a comparative analysis of reproductive isolation in California Jewelflowers (Streptanthus, s.l., Brassicaceae) by quantifying potential barriers to gene flow at multiple life history stages in 39 species pairs spanning five million years of evolutionary divergence. We quantified nine potential pre- and postzygotic barriers and explored patterns of reproductive isolation in relation to genetic distance. Intrinsic postzygotic isolation was initially weak, increased at intermediate genetic distances, and reached a threshold characterized by complete genetic incompatibility. Climatic niche differences were strong at shallow genetic distances, and species pairs with overlapping ranges showed slight but appreciable phenological isolation, highlighting the potential for ecological barriers to contribute to speciation. Geographic analyses suggest that speciation is not regionally allopatric in the California Jewelflowers, as recently diverged taxa occur in relatively close proximity and display substantial range overlap. Young pairs are characterized by incomplete intrinsic postzygotic isolation, suggesting that extrinsic barriers or fine-scale spatial segregation are more important early in the divergence process than genetic incompatibilities. © 2018 The Author(s). Evolution © 2018 The Society for the Study of Evolution.

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

Characterization of groundwater composition in Punjab state with special emphasis on uranium content, speciation and mobility

Energy Technology Data Exchange (ETDEWEB)

Kumar, Ajay; Rout, Sabyasachi; Mishra, Manish K.; Ravi, P.M. [Bhabha Atomic Reseach Centre, Mumbai (India). Health Physics Div.; Tripathi, R.M. [Bhabha Atomic Reseach Centre, Mumbai (India). Environmental Assessment Div.; Ghosh, A.K. [Bhabha Atomic Reseach Centre, Mumbai (India). Health, Safety and Environmental Group

2014-04-01

Groundwaters (borewell and handpump) were sampled from two districts (Bathinda and Mansa) of Punjab state and analyzed for their major ionic concentrations and uranium isotope compositions in order to assess the possible origins of the waters and water-rock interactions that occurred in the deep aquifer system. The major ionic concentrations of waters were plotted on a Piper diagram and grouped into four dominant hydrochemical facies as (Na+K)-SO{sub 4}+Cl type (69%-73%), (Ca+Mg)-SO{sub 4}+Cl type (6% - 21%), (Ca+Mg)-HCO{sub 3} type (4% - 6%) and (Na+K)-HCO{sub 3} type (2% - 19%). It was observed that mobility of uranium in groundwater was very much influenced by TDS (total dissolved solids). To investigate the various mechanisms for deriving the elevated uranium concentrations in groundwater, {sup 234}U/{sup 238}U activity ratios (ARs) were calculated using the determined activity levels of {sup 234}U and {sup 238}U. The mean ARs was found to be near unity (i.e. secular equilibrium) in the study regions confirmed that uranium in groundwaters was mainly resulted from its host/parent rocks through weathering processes. The concentration of HCO{sub 3}{sup -} in ground water showed one order of magnitude higher than the total dissolved SiO{sub 2} indicates that carbonate weathering was the dominant process due to major water-rock interaction. The uranium speciation in groundwaters was investigated by an equilibrium model calculation using MEDUSA (make equilibrium diagrams using sophisticated algorithms) under the influence of redox conditions and complexant concentration. At the observed range of pH values, the predominant redox speciation of uranium was observed as hydroxo-carbonato complexes of (UO{sub 2}){sub 2}(CO{sub 3})(OH){sub 3}{sup -} and hydroxyl complexes of UO{sub 2}(OH){sub 3}{sup -} which might be caused for increasing the solubility of uranium. Due to very low concentration of phosphate in groundwater, its effects on U(VI)-aqueous speciation was

Revision of Drusinae subfamily (Trichoptera, Limnephilidae: divergence by paraproct and paramere: speciation in isolation by integration

Directory of Open Access Journals (Sweden)

Oláh, János

2017-08-01

Full Text Available In the last few years we have described over 70 new incipient sibling limnephild species applying the discovered Trichoptera speciation traits of the paraproct and paramere for species recognition and delimitation. In this revision on Drusinae subfamily, comprising 177 species, we have applied these subtle, but rapid and stable speciation traits and described 49 new sibling species from the “well studied” European mountain ranges. Discussing the theoretical background we have elaborated and adapted a new character state ranking system of phenomics to revise the long-neglected taxonomy of the Drusinae subfamily and synonymised the Cryptothrix, Monocentra, Metanoea, Leptodrusus, Anomalopterygella, Hadimina genera with the Drusus genus. These old genera of artificial constructs were established exclusively by divergences of secondary sexual traits known already to have only species level ranking value. According to our new character ranking system in the Drusinae subfamily, beside the Drusus genus, only the Ecclisopteryx genus has been retained having robust generic level divegences of paraproct loss and ancestral duplication of spine organising centre on the paramere pattern. Speciation trait function of the peg-packed surface on the paraproct head in Drusus genus moved to the gonopod apices and integrated into variously shaped stimulatory organ in the Ecclisopteryx genus. In the Drusus genus the ancestral divergence of the single spine organising centre has integrated 11 species groups with remarkably stable paramere spine pattern. Based upon ancestral divergences in the paraproct architecture we have differenciated 28 species complexes inside the 11 species groups. The delineation of the 163 mostly incipient siblings species, inside the 28 species complexes with 44 new Drusus species, was based primarily on the divergences of speciation trait, that is in the stimulatory head shape of the apical arms on the dorsal branches of the paraproct

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....

Functional speciation of metal-dissolved organic matter complexes by size exclusion chromatography coupled to inductively coupled plasma mass spectrometry and deconvolution analysis

International Nuclear Information System (INIS)

Laborda, Francisco; Ruiz-Begueria, Sergio; Bolea, Eduardo; Castillo, Juan R.

2009-01-01

High performance size exclusion chromatography coupled to inductively coupled plasma mass spectrometry (HP-SEC-ICP-MS), in combination with deconvolution analysis, has been used to obtain multielemental qualitative and quantitative information about the distributions of metal complexes with different forms of natural dissolved organic matter (DOM). High performance size exclusion chromatography coupled to inductively coupled plasma mass spectrometry chromatograms only provide continuous distributions of metals with respect to molecular masses, due to the high heterogeneity of dissolved organic matter, which consists of humic substances as well as biomolecules and other organic compounds. A functional speciation approach, based on the determination of the metals associated to different groups of homologous compounds, has been followed. Dissolved organic matter groups of homologous compounds are isolated from the aqueous samples under study and their high performance size exclusion chromatography coupled to inductively coupled plasma mass spectrometry elution profiles fitted to model Gaussian peaks, characterized by their respective retention times and peak widths. High performance size exclusion chromatography coupled to inductively coupled plasma mass spectrometry chromatograms of the samples are deconvoluted with respect to these model Gaussian peaks. This methodology has been applied to the characterization of metal-dissolved organic matter complexes in compost leachates. The most significant groups of homologous compounds involved in the complexation of metals in the compost leachates studied have been hydrophobic acids (humic and fulvic acids) and low molecular mass hydrophilic compounds. The environmental significance of these compounds is related to the higher biodegradability of the low molecular mass hydrophilic compounds and the lower mobility of humic acids. In general, the hydrophilic compounds accounted for the complexation of around 50% of the leached

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)

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.

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

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:...

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

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.

Near field chemical speciation: the reaction of uranium and thorium with Hanford basalt and elevated pH

International Nuclear Information System (INIS)

Perry, D.L.

1984-01-01

The hydrolysis of radionuclides such as thorium and uranium and their subsequent chemisorption on Hanford basalt have been studied using a variety of techniques, including x-ray photoelectron and infrared spectroscopy. Data obtained to date indicate mixed complexes of uranium and thorium to be on the basalt surface, the complexes being radionuclide oxides, hydrated oxides (hydroxides), and carbonates. These findings are discussed with respect to their importance for input for models describing speciation and dissolution processes involving nuclear waste repository materials such as Hanford basalt. 5 figures, 2 tables

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.)

Chromium speciation in environmental samples using a solid phase spectrophotometric method

Science.gov (United States)

Amin, Alaa S.; Kassem, Mohammed A.

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.

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 ...

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.)

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.)

Genetic structure and bio-climatic modeling support allopatric over parapatric speciation along a latitudinal gradient

Directory of Open Access Journals (Sweden)

Rossetto Maurizio

2012-08-01

an optimum number of five clusters corresponding to the four recognised species with the additional division of T. speciosissima into populations north and south of the Shoalhaven River valley. Unexpectedly, the northern disjunct population of T. oreades grouped with T. mongaensis and was identified as a hybrid swarm by the Bayesian assignment test implemented in NewHybrids. Present day and LGM environmental niche models differed dramatically, suggesting that distributions of all species had repeatedly expanded and contracted in response to Pleistocene climatic oscillations and confirming strongly marked historical distributional gaps among taxes. Conclusions Genetic structure and bio-climatic modeling results are more consistent with a history of allopatric speciation followed by repeated episodes of secondary contact and localised hybridisation, rather than with parapatric speciation. This study on Telopea shows that the evidence for temporal exclusion of gene flow can be found even outside obvious geographical contexts, and that it is possible to make significant progress towards excluding parapatric speciation as a contributing evolutionary process.

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.

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.

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.

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.)

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)

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

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

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.

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

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)

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...

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

Ternary uranium(VI) carbonato humate complex studied by cryo-TRLFS

International Nuclear Information System (INIS)

Steudtner, R.; Sachs, S.; Schmeide, K.; Brendler, V.; Bernhard, G.

2011-01-01

The complex formation of U(VI) with humic acid (HA) in the presence of carbonate was studied by time-resolved laser-induced fluorescence spectroscopy at low temperature (cryo-TRLFS) at pH 8.5. In the presence of HA, a decrease of the luminescence intensity of U(VI) and no shift of the emission band maxima in comparison to the luminescence spectrum of the UO 2 (CO 3 ) 3 4- complex, the dominating U(VI) species under the applied experimental conditions in the absence of HA, was observed. The formation of a ternary U(VI) carbonato humate complex of the type UO 2 (CO 3 ) 2 HA(II) 4- starting from UO 2 (CO 3 ) 3 4- was concluded from the luminescence data. For this complex a complex stability constant of log K=2.83 ± 0.17 was determined. Slope analysis resulted in a slope of 1.12 ± 0.11, which verifies the postulated complexation reaction. The results agree very well with literature data. Speciation calculations show that the formation of the ternary U(VI) carbonato humate complex can significantly influence the U(VI) speciation under environmental conditions. (orig.)

Wide distribution and ancient evolutionary history of simian foamy viruses in New World primates.

Science.gov (United States)

Ghersi, Bruno M; Jia, Hongwei; Aiewsakun, Pakorn; Katzourakis, Aris; Mendoza, Patricia; Bausch, Daniel G; Kasper, Matthew R; Montgomery, Joel M; Switzer, William M

2015-10-29

Although simian foamy viruses (SFV) are the only exogenous retroviruses to infect New World monkeys (NWMs), little is known about their evolutionary history and epidemiology. Previous reports show distinct SFVs among NWMs but were limited to small numbers of captive or wild monkeys from five (Cebus, Saimiri, Ateles, Alouatta, and Callithrix) of the 15 NWM genera. Other studies also used only PCR testing or serological assays with limited validation and may have missed infection in some species. We developed and validated new serological and PCR assays to determine the prevalence of SFV in blood specimens from a large number of captive NWMs in the US (n = 274) and in captive and wild-caught NWMs (n = 236) in Peruvian zoos, rescue centers, and illegal trade markets. Phylogenetic and co-speciation reconciliation analyses of new SFV polymerase (pol) and host mitochondrial cytochrome B sequences, were performed to infer SFV and host co-evolutionary histories. 124/274 (45.2 %) of NWMs captive in the US and 59/157 (37.5 %) of captive and wild-caught NWMs in Peru were SFV WB-positive representing 11 different genera (Alouatta, Aotus, Ateles, Cacajao, Callithrix, Cebus, Lagothrix, Leontopithecus, Pithecia, Saguinus and Saimiri). Seroprevalences were lower at rescue centers (10/53, 18.9 %) compared to zoos (46/97, 47.4 %) and illegal trade markets (3/7, 8/19, 42.9 %) in Peru. Analyses showed that the trees of NWM hosts and SFVs have remarkably similar topologies at the level of species and sub-populations suggestive of co-speciation. Phylogenetic reconciliation confirmed 12 co-speciation events (p history of SFV in NWMs at the species level. Additional studies are necessary to further explore the epidemiology and natural history of SFV infection of NWMs and to determine the zoonotic potential for persons exposed to infected monkeys in captivity and in the wild.

Speciation with gene flow in whiptail lizards from a Neotropical xeric biome.

Science.gov (United States)

Oliveira, Eliana F; Gehara, Marcelo; São-Pedro, Vinícius A; Chen, Xin; Myers, Edward A; Burbrink, Frank T; Mesquita, Daniel O; Garda, Adrian A; Colli, Guarino R; Rodrigues, Miguel T; Arias, Federico J; Zaher, Hussam; Santos, Rodrigo M L; Costa, Gabriel C

2015-12-01

Two main hypotheses have been proposed to explain the diversification of the Caatinga biota. The riverine barrier hypothesis (RBH) claims that the São Francisco River (SFR) is a major biogeographic barrier to gene flow. The Pleistocene climatic fluctuation hypothesis (PCH) states that gene flow, geographic genetic structure and demographic signatures on endemic Caatinga taxa were influenced by Quaternary climate fluctuation cycles. Herein, we analyse genetic diversity and structure, phylogeographic history, and diversification of a widespread Caatinga lizard (Cnemidophorus ocellifer) based on large geographical sampling for multiple loci to test the predictions derived from the RBH and PCH. We inferred two well-delimited lineages (Northeast and Southwest) that have diverged along the Cerrado-Caatinga border during the Mid-Late Miocene (6-14 Ma) despite the presence of gene flow. We reject both major hypotheses proposed to explain diversification in the Caatinga. Surprisingly, our results revealed a striking complex diversification pattern where the Northeast lineage originated as a founder effect from a few individuals located along the edge of the Southwest lineage that eventually expanded throughout the Caatinga. The Southwest lineage is more diverse, older and associated with the Cerrado-Caatinga boundaries. Finally, we suggest that C. ocellifer from the Caatinga is composed of two distinct species. Our data support speciation in the presence of gene flow and highlight the role of environmental gradients in the diversification process. © 2015 John Wiley & Sons Ltd.

Chemical speciation modelling of groundwater in a shallow glacial sand aquifer part 1 General parameters

OpenAIRE

Falck, W.E.; Quinn, G.W.; Duffield, J.R.; Williams, D.R.

1988-01-01

The aim of the work detailed in this report has been to gain a better understanding of the speciation chemistry controlling the aqueous chemical forms of elements and compounds normally present in groundwaters found at the BGS in situ migration experiment at Drigg, Cumbria. This will form the basis of future modelling studies designed to interpret in situ tracer experiments using 60Co in the presence of naturally occurring organic complexants. Total element concentrations in re...

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

International Nuclear Information System (INIS)

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

2014-01-01

In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO 4 , chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO 3 . In rye-grass, the changes in Pb speciation were even more egregious: Pb–cell wall and Pb–organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better

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

Energy Technology Data Exchange (ETDEWEB)

Schreck, Eva [Université de Toulouse, INP, UPS, EcoLab (Laboratoire Ecologie Fonctionnelle et Environnement), ENSAT, Avenue de l' Agrobiopole, 31326 Castanet-Tolosan (France); CNRS, EcoLab, 31326 Castanet-Tolosan (France); Géosciences Environnement Toulouse (GET), Observatoire Midi Pyrénées, Université de Toulouse, CNRS, IRD, 14 Avenue E. Belin, F-31400 Toulouse (France); Dappe, Vincent [LASIR (UMR CNRS 8516), Université de Lille 1, Bât. C5, 59655 Villeneuve d' Ascq Cedex (France); Sarret, Géraldine [ISTerre, UMR 5275, Université Grenoble I, CNRS, F-38041 Grenoble (France); Sobanska, Sophie [LASIR (UMR CNRS 8516), Université de Lille 1, Bât. C5, 59655 Villeneuve d' Ascq Cedex (France); Nowak, Dorota; Nowak, Jakub; Stefaniak, Elżbieta Anna [Department of Chemistry, John Paul II Catholic University of Lublin, Al. Kraśnicka 102, 20-718 Lublin (Poland); Magnin, Valérie [ISTerre, UMR 5275, Université Grenoble I, CNRS, F-38041 Grenoble (France); Ranieri, Vincent [CEA-INAC, 17 rue des Martyrs, 38054 Grenoble Cedex 9 (France); Dumat, Camille, E-mail: camille.dumat@ensat.fr [Université de Toulouse, INP, UPS, EcoLab (Laboratoire Ecologie Fonctionnelle et Environnement), ENSAT, Avenue de l' Agrobiopole, 31326 Castanet-Tolosan (France); CNRS, EcoLab, 31326 Castanet-Tolosan (France)

2014-04-01

In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO{sub 4}, chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO{sub 3}. In rye-grass, the changes in Pb speciation were even more egregious: Pb–cell wall and Pb–organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to

Spectroscopy of plutonium-organic complexes

International Nuclear Information System (INIS)

Richmann, M.K.; Reed, D.T.

1995-01-01

Information on the spectroscopy of plutonium-organic complexes is needed to help establish the speciation of these complexes under environmentally relevant conditions. Laser photoacoustic spectroscopy (LPAS) and absorption spectrometry were used to characterize the Pu(IV)-citrate and Pu(IV)-nitrilotriacetic acid (NTA) complexes at concentrations of 10 -3 --10 -7 M in aqueous solution. Good agreement was observed between the band shape of the LPAS and absorption spectra for the Pu(IV)-NTA complex. Agreement for the Pu(IV)-citrate complex was not quite as good. In both cases, a linear dependence of the LPAS signal on laser power and total concentration of the complexes was noted. This work is part of an ongoing research effort to study key subsurface interactions of plutonium-organic complexes

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

Comparative Analysis of Satellite DNA in the Drosophila melanogaster Species Complex

Directory of Open Access Journals (Sweden)

Madhav Jagannathan

2017-02-01

Full Text Available Satellite DNAs are highly repetitive sequences that account for the majority of constitutive heterochromatin in many eukaryotic genomes. It is widely recognized that sequences and locations of satellite DNAs are highly divergent even in closely related species, contributing to the hypothesis that satellite DNA differences may underlie speciation. However, due to its repetitive nature, the mapping of satellite DNAs has been mostly left out of recent genomics analyses, hampering the use of molecular genetics techniques to better understand their role in speciation and evolution. Satellite DNAs are most extensively and comprehensively mapped in Drosophila melanogaster, a species that is also an excellent model system with which to study speciation. Yet the lack of comprehensive knowledge regarding satellite DNA identity and location in its sibling species (D. simulans, D. mauritiana, and D. sechellia has prevented the full utilization of D. melanogaster in studying speciation. To overcome this problem, we initiated the mapping of satellite DNAs on the genomes of the D. melanogaster species complex (D. melanogaster, D. simulans, D. mauritiana, and D. sechellia using multi-color fluorescent in situ hybridization (FISH probes. Our study confirms a striking divergence of satellite DNAs in the D. melanogaster species complex, even among the closely related species of the D. simulans clade (D. simulans, D. mauritiana, and D. sechellia, and suggests the presence of unidentified satellite sequences in these species.

Biomic specialization and speciation rates in ruminants (Cetartiodactyla, Mammalia): a test of the resource-use hypothesis at the global scale.

Science.gov (United States)

Cantalapiedra, Juan L; Hernández Fernández, Manuel; Morales, Jorge

2011-01-01

The resource-use hypothesis proposed by E.S. Vrba predicts that specialist species have higher speciation and extinction rates than generalists because they are more susceptible to environmental changes and vicariance. In this work, we test some of the predictions derived from this hypothesis on the 197 extant and recently extinct species of Ruminantia (Cetartiodactyla, Mammalia) using the biomic specialization index (BSI) of each species, which is based on its distribution within different biomes. We ran 10000 Monte Carlo simulations of our data in order to get a null distribution of BSI values against which to contrast the observed data. Additionally, we drew on a supertree of the ruminants and a phylogenetic likelihood-based method (QuaSSE) for testing whether the degree of biomic specialization affects speciation rates in ruminant lineages. Our results are consistent with the predictions of the resource-use hypothesis, which foretells a higher speciation rate of lineages restricted to a single biome (BSI = 1) and higher frequency of specialist species in biomes that underwent high degree of contraction and fragmentation during climatic cycles. Bovids and deer present differential specialization across biomes; cervids show higher specialization in biomes with a marked hydric seasonality (tropical deciduous woodlands and schlerophyllous woodlands), while bovids present higher specialization in a greater variety of biomes. This might be the result of divergent physiological constraints as well as a different biogeographic and evolutionary history.

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

Bulk solubility and speciation of plutonium(VI) in phosphate-containing solutions

International Nuclear Information System (INIS)

Weger, H.T.; Okajima, S.; Cunnane, J.C.; Reed, D.T.

1992-01-01

The solubility and speciation of Pu(VI) with phosphate as a function of pH was investigated to determine the ability of phosphate to act as an actinide getter. The general properties were first investigated and are reported here with the goal of performing more quantitative experiments in the future. Solubility was approached from oversaturation at initial pH = 4, 10 and 13.4. Absorption spectra were recorded, the solution filtered and the filtrate counted. Absorption spectra were obtained at varying phosphate concentrations and at pH of 2.7 to 11.9. The effect of complexation on the 833 mn Pu(VI) band was characterized. Evidence for three phosphate complexes was obtained for pH -5 to 10 -6 M Pu(VI) was measured in the filtrate at pH ≤ 10 that were passed through a 50 mn filter. Pu(VI) complexes with phosphate over hydroxide at pH ≤ 11.6, but at pH ≥ 11.9, only hydrolyzed Pu(VI) was detected. At pH = 12, the concentration of Pu(VI) was as high as 10 -4 M

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

Energy Technology Data Exchange (ETDEWEB)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

2017-06-01

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth’s history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES) spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes—many containing organic ligands—we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H2S(aq)] < 11 µM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO3, MoOxS4-x2- (intermediate thiomolybdates), and [MoOx(cat)4-x]2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS42- (tetrathiomolybdate).

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...

Speciation of chromium by dispersive liquid–liquid microextraction followed by laser-induced breakdown spectrometry detection (DLLME–LIBS)

OpenAIRE

Gaubeur, Ivanise; Aguirre Pastor, Miguel Ángel; Kovachev, Nikolay; Hidalgo Núñez, Montserrat; Canals Hernández, Antonio

2015-01-01

In this study, an analytical methodology based on a combination of dispersive liquid–liquid microextraction with laser-induced breakdown spectrometry was evaluated for simultaneous pre-concentration, speciation and detection of Cr. The microextraction procedure was based on the injection of appropriated quantities of 1-undecanol and ethanol into a sample solution containing the complexes formed between Cr(VI) and diethyldithiocarbamate (DDTC). The main experimental factors affecting the compl...

Detection and speciation of transuranium elements in synthetic groundwater via pulsed-laser excitation

International Nuclear Information System (INIS)

Beitz, J.V.; Bowers, D.L.; Doxtader, M.M.; Maroni, V.A.; Reed, D.T.

1987-01-01

High sensitivity methods for detection and speciation of complexed transuranium ions in synthetic basalt groundwater, and simplified analogs, are being developed which exploit advances in pulsed laser technology. The first demonstration of high sensitivity detection of a transuranium ion at temperatures significantly above ambient is reported using laser photoacoustic spectroscopy (LPAS). The existence of enhanced LPAS signal amplitudes with increasing temperature in aqueous solution is confirmed in LPAS spectra recorded at 30 C, 60 C and 90 C using micromolar concentrations of /sup 241/Am/sup 3+/. A detection sensitivity of 8.5 parts per trillion (weight basis) of /sup 244/Cm/sup 3+/ in a simplified basalt groundwater at 22 C has been achieved using laser-induced fluorescence spectroscopy (LIF). This corresponds to 1 x 10/sup 8/ Cm/sup 3+/ ions in the laser beam. The detailed spectroscopic information obtained by this method points to the existence of previously unobserved Cm/sup 3+/ species. A brief assessment of the applicability and sensitivity of LPAS and LIF methods for speciating transuranium ions in near-neutral pH aqueous solution, such as the groundwater expected in a basalt nuclear waste repository, is presented. 27 refs., 3 figs

Molecular Phylogeny and Zoogeography of the Capoeta damascina Species Complex (Pisces: Teleostei: Cyprinidae.

Directory of Open Access Journals (Sweden)

Nisreen Alwan

Full Text Available Capoeta damascina was earlier considered by many authors as one of the most common freshwater fish species found throughout the Levant, Mesopotamia, Turkey, and Iran. However, owing to a high variation in morphological characters among and within its various populations, 17 nominal species were described, several of which were regarded as valid by subsequent revising authors. Capoeta damascina proved to be a complex of closely related species, which had been poorly studied. The current study aims at defining C. damascina and the C. damascina species complex. It investigates phylogenetic relationships among the various members of the C. damascina complex, based on mitochondrial and nuclear DNA sequences. Phylogenetic relationships were projected against paleogeographical events to interpret the geographic distribution of the taxa under consideration in relation to the area's geological history. Samples were obtained from throughout the geographic range and were subjected to genetic analyses, using two molecular markers targeting the mitochondrial cytochrome oxidase I (n = 103 and the two adjacent divergence regions (D1-D2 of the nuclear 28S rRNA genes (n = 65. Six closely related species were recognized within the C. damascina complex, constituting two main lineages: A western lineage represented by C. caelestis, C. damascina, and C. umbla and an eastern lineage represented by C. buhsei, C. coadi, and C. saadii. The results indicate that speciation of these taxa is rather a recent event. Dispersal occurred during the Pleistocene, resulting in present-day distribution patterns. A coherent picture of the phylogenetic relationships and evolutionary history of the C. damascina species complex is drawn, explaining the current patterns of distribution as a result of paleogeographic events and ecological adaptations.

Molecular Phylogeny and Zoogeography of the Capoeta damascina Species Complex (Pisces: Teleostei: Cyprinidae).

Science.gov (United States)

Alwan, Nisreen; Esmaeili, Hamid-Reza; Krupp, Friedhelm

2016-01-01

Capoeta damascina was earlier considered by many authors as one of the most common freshwater fish species found throughout the Levant, Mesopotamia, Turkey, and Iran. However, owing to a high variation in morphological characters among and within its various populations, 17 nominal species were described, several of which were regarded as valid by subsequent revising authors. Capoeta damascina proved to be a complex of closely related species, which had been poorly studied. The current study aims at defining C. damascina and the C. damascina species complex. It investigates phylogenetic relationships among the various members of the C. damascina complex, based on mitochondrial and nuclear DNA sequences. Phylogenetic relationships were projected against paleogeographical events to interpret the geographic distribution of the taxa under consideration in relation to the area's geological history. Samples were obtained from throughout the geographic range and were subjected to genetic analyses, using two molecular markers targeting the mitochondrial cytochrome oxidase I (n = 103) and the two adjacent divergence regions (D1-D2) of the nuclear 28S rRNA genes (n = 65). Six closely related species were recognized within the C. damascina complex, constituting two main lineages: A western lineage represented by C. caelestis, C. damascina, and C. umbla and an eastern lineage represented by C. buhsei, C. coadi, and C. saadii. The results indicate that speciation of these taxa is rather a recent event. Dispersal occurred during the Pleistocene, resulting in present-day distribution patterns. A coherent picture of the phylogenetic relationships and evolutionary history of the C. damascina species complex is drawn, explaining the current patterns of distribution as a result of paleogeographic events and ecological adaptations.

Limnephilid taxa revised by speciation traits: Rhadicoleptus, Isogamus, Melampophylax genera, Chaetopteryx rugulosa, Psilopteryx psorosa species groups, Drusus bolivari, Annitella kosciuszkii species complexes (Trichoptera: Limnephilidae)

Czech Academy of Sciences Publication Activity Database

Oláh, J.; Chvojka, P.; Coppa, G.; Godunko, Roman J.; Lodovici, O.; Majecka, K.; Majecki, J.; Szczęsny, B.; Urbanic, G.; Valle, M.

2015-01-01

Roč. 46, č. 1 (2015), s. 3-117 ISSN 0237-5419 Institutional support: RVO:60077344 Keywords : speciation traits * neutral and adaptive molecular markers * neutral and adaptive traits Subject RIV: EG - Zoology

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

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.

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 ...

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.

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.

Speciation of Bactrocera dorsalis complex based on aedeagus length

International Nuclear Information System (INIS)

Osamu Iwahashi

2000-01-01

A species complex of Bactrocera dorsalis (Hendel) in Southeast Asia is composed of 52 species (Drew and Hancock, 1994) and while some of these species are economically very important, distinguishing them based on morphological characters has been difficult (White and Elson-Harris 1992). Specifically, there is considerable difficulty in differentiating between males of two pairs of sympatric species, B. philippinensis Drew and Hancock/B. occipitalis (Bezzi) in the Philippines and B. carambolae Drew and Hancock/B. papayae Drew and Hancock in Indonesia. This may be, in part, because the evolutionary processes within this species complex are still very dynamic, and that natural hybridisation between sympatric species pairs might be occurring on a regular basis (He and Haymer 1997). Iwaizumi et al. (1997) developed a simple method to differentiate the two sets of sympatric species based on aedeagus lengths. However, these flies had been reared artificially under laboratory conditions and only a small number of specimens (n=5) was used. Consequently, they were not able to obtain a frequency distribution of the aedeagus length for each species. Iwahashi (1998) measured a larger number of wild flies collected on Guimaras Is, Philippines, and found that flies with the aedeagus length of 2.89 mm are B. philippinensis. Iwahashi (1999) also showed that the measurement of the aedeagal length of fruit flies is a reliable characteristic for distinguishing between the 2 sympatric species pairs in the B. dorsalis complex. This being so, it may also be interesting to interpret phylogenetic relationships among B. dorsalis complex species based on the aedeagus length. Thus, aedeagus lengths of different populations of five B. dorsalis complex species are measured and their relationships discussed

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...

Lability of nanoparticulate metal complexes in electrochemical speciation analysis

DEFF Research Database (Denmark)

van Leeuwen, Herman P.; Town, Raewyn M.

2016-01-01

Lability concepts are elaborated for metal complexes with soft (3D) and hard (2D) aqueous nanoparticles. In the presence of a non-equilibrium sensor, e.g. a voltammetric electrode, the notion of lability for nanoparticulate metal complexes, M-NP, reflects the ability of the M-NP to maintain...... equilibrium with the reduced concentration of the electroactive free M2+ in its diffusion layer. Since the metal ion binding sites are confined to the NP body, the conventional reaction layer in the form of a layer adjacent to the electrode surface is immaterial. Instead an intraparticulate reaction zone may...... of the electrochemical technique is crucial in the lability towards the electrode surface. In contrast, for nanoparticulate complexes it is the dynamics of the exchange of the electroactive metal ion with the surrounding medium that governs the effective lability towards the electrode surface....

The effect of advanced treatment of sewage effluents on metal speciation and (bio)availability.

Science.gov (United States)

Peters, A; Merrington, G; Leverett, D; Ellor, B; Lofts, S; Gravell, A

2014-02-01

The bioavailability of metals can be strongly influenced by dissolved organic carbon (DOC). Wastewater treatment effluents add considerable quantities of DOC and metals to receiving waters, and as effluent controls become more stringent advanced effluent treatments may be needed. We assessed the effects of two types of advanced treatment processes on metal availability in wastewater effluents. Trace metal availability was assessed using diffuse gradients in thin films and predicted through speciation modelling. The results show little difference in metal availability post-advanced treatment. EDTA-like compounds are important metal complexants in the effluents.

Composition of COH fluids at 1 GPa: an experimental study on speciation and solubility

Science.gov (United States)

Tiraboschi, Carla; Tumiati, Simone; Recchia, Sandro; Ulmer, Peter; Pettke, Thomas; Fumagalli, Patrizia; Poli, Stefano

2014-05-01

COH fluids play a fundamental role in many geological processes, controlling the location of melting in subduction zones and promoting mass transfer from the subducting litosphere to the overlying mantle wedge. The properties of COH fluids are strictly dependent on the composition of the fluid in subduction systems, i.e., the speciation of the volatile components of the fluid itself and the presence of solutes deriving from the dissolution of rock-forming minerals. In the scientific literature, the speciation of COH fluids has been generally determined through thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4), equations that do not consider the complexity related to dissolution processes, which are substantially unexplored in COH fluids and limited so far to aqueous fluids (Newton & Manning, 2002). The aim of this work is to investigate experimentally the speciation and the dissolution of mantle minerals in carbon-saturated COH fluids at buffered fO2 conditions. Our experimental approach relies on two different techniques: 1) analysis by means of quadrupole mass spectrometer (QMS) of the fluids from pierced run capsules to retrieve speciation of volatile components and 2) analysis of frozen COH fluid with laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) to measure the amount of solutes. Experiments were conducted at pressure of 1 GPa and temperatures from 800 to 900° C using a rocking piston cylinder apparatus. Mantle minerals in equilibrium with COH fluid are represented by synthetic forsterite. fO2 conditions were controlled using the double capsule technique and NNO buffer (ΔFMQ=-0.61 at 800° C; ΔFMQ =-0.98 at 900° C). For the speciation experiments, oxalic acid dihydrate and graphite have been used to generate carbon-saturated COH fluid. The speciation was determined by analyzing the quenched COH fluid, retrieved by piercing the capsule in a gas-tight vessel at T =80° C and

Ternary uranium(VI) carbonato humate complex studied by cryo-TRLFS

Energy Technology Data Exchange (ETDEWEB)

Steudtner, R.; Sachs, S.; Schmeide, K.; Brendler, V.; Bernhard, G. [Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany). Inst. of Radiochemistry

2011-07-01

The complex formation of U(VI) with humic acid (HA) in the presence of carbonate was studied by time-resolved laser-induced fluorescence spectroscopy at low temperature (cryo-TRLFS) at pH 8.5. In the presence of HA, a decrease of the luminescence intensity of U(VI) and no shift of the emission band maxima in comparison to the luminescence spectrum of the UO{sub 2}(CO{sub 3}){sub 3}{sup 4-} complex, the dominating U(VI) species under the applied experimental conditions in the absence of HA, was observed. The formation of a ternary U(VI) carbonato humate complex of the type UO{sub 2}(CO{sub 3}){sub 2}HA(II){sup 4-} starting from UO{sub 2}(CO{sub 3}){sub 3}{sup 4-} was concluded from the luminescence data. For this complex a complex stability constant of log K=2.83 {+-} 0.17 was determined. Slope analysis resulted in a slope of 1.12 {+-} 0.11, which verifies the postulated complexation reaction. The results agree very well with literature data. Speciation calculations show that the formation of the ternary U(VI) carbonato humate complex can significantly influence the U(VI) speciation under environmental conditions. (orig.)

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-11-16

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-06-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-06-01

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

Speciation and the Latitudinal Diversity Gradient: Insights from the Global Distribution of Endemic Fish.

Science.gov (United States)

Hanly, Patrick J; Mittelbach, Gary G; Schemske, Douglas W

2017-06-01

The nearly universal pattern that species richness increases from the poles to the equator (the latitudinal diversity gradient [LDG]) has been of intense interest since its discovery by early natural-history explorers. Among the many hypotheses proposed to explain the LDG, latitudinal variation in (1) productivity, (2) time and area available for diversification, and (3) speciation and/or extinction rates have recently received the most attention. Because tropical regions are older and were formerly more widespread, these factors are often intertwined, hampering efforts to distinguish their relative contributions to the LDG. Here we examine the global distribution of endemic lake fishes to determine how lake age, area, and latitude each affect the probability of speciation and the extent of diversification occurring within a lake. We analyzed the distribution of endemic fishes worldwide (1,933 species and subspecies from 47 families in 2,746 lakes) and find that the probability of a lake containing an endemic species and the total number of endemics per lake increase with lake age and area and decrease with latitude. Moreover, the geographic locations of endemics in 34 of 41 families are found at lower latitudes than those of nonendemics. We propose that the greater diversification of fish at low latitudes may be driven in part by ecological opportunities promoted by tropical climates and by the coevolution of species interactions.

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.

Not a simple case - A first comprehensive phylogenetic hypothesis for the Midas cichlid complex in Nicaragua (Teleostei: Cichlidae: Amphilophus).

Science.gov (United States)

Geiger, Matthias F; McCrary, Jeffrey K; Schliewen, Ulrich K

2010-09-01

Nicaraguan Midas cichlids from crater lakes have recently attracted attention as potential model systems for speciation research, but no attempt has been made to comprehensively reconstruct phylogenetic relationships of this highly diverse and recently evolved species complex. We present a first AFLP (2793 loci) and mtDNA based phylogenetic hypothesis including all described and several undescribed species from six crater lakes (Apoyeque, Apoyo, Asososca Leon, Masaya, Tiscapa and Xiloá), the two great Lakes Managua and Nicaragua and the San Juan River. Our analyses demonstrate that the relationships between the Midas cichlid members are complex, and that phylogenetic information from different markers and methods do not always yield congruent results. Nevertheless, monophyly support for crater lake assemblages from Lakes Apoyeque, Apoyo, A. Leon is high as compared to those from L. Xiloá indicating occurrence of sympatric speciation. Further, we demonstrate that a 'three species' concept for the Midas cichlid complex is inapplicable and consequently that an individualized and voucher based approach in speciation research of the Midas cichlid complex is necessary at least as long as there is no comprehensive revision of the species complex available. Copyright 2010 Elsevier Inc. All rights reserved.

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.

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Science.gov (United States)

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

Probabilities in quantum cosmological models: A decoherent histories analysis using a complex potential

International Nuclear Information System (INIS)

Halliwell, J. J.

2009-01-01

In the quantization of simple cosmological models (minisuperspace models) described by the Wheeler-DeWitt equation, an important step is the construction, from the wave function, of a probability distribution answering various questions of physical interest, such as the probability of the system entering a given region of configuration space at any stage in its entire history. A standard but heuristic procedure is to use the flux of (components of) the wave function in a WKB approximation. This gives sensible semiclassical results but lacks an underlying operator formalism. In this paper, we address the issue of constructing probability distributions linked to the Wheeler-DeWitt equation using the decoherent histories approach to quantum theory. The key step is the construction of class operators characterizing questions of physical interest. Taking advantage of a recent decoherent histories analysis of the arrival time problem in nonrelativistic quantum mechanics, we show that the appropriate class operators in quantum cosmology are readily constructed using a complex potential. The class operator for not entering a region of configuration space is given by the S matrix for scattering off a complex potential localized in that region. We thus derive the class operators for entering one or more regions in configuration space. The class operators commute with the Hamiltonian, have a sensible classical limit, and are closely related to an intersection number operator. The definitions of class operators given here handle the key case in which the underlying classical system has multiple crossings of the boundaries of the regions of interest. We show that oscillatory WKB solutions to the Wheeler-DeWitt equation give approximate decoherence of histories, as do superpositions of WKB solutions, as long as the regions of configuration space are sufficiently large. The corresponding probabilities coincide, in a semiclassical approximation, with standard heuristic procedures

Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles.

Science.gov (United States)

Formentini, Thiago Augusto; Legros, Samuel; Fernandes, Cristovão Vicente Scapulatempo; Pinheiro, Adilson; Le Bars, Maureen; Levard, Clément; Mallmann, Fábio Joel Kochem; da Veiga, Milton; Doelsch, Emmanuel

2017-03-01

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biogeochemical controls on the speciation and aquatic toxicity of vanadium and other metals in sediments from a river reservoir

Energy Technology Data Exchange (ETDEWEB)

Nedrich, Sara M.; Chappaz, Anthony; Hudson, Michelle L.; Brown, Steven S.; Burton, G. Allen

2018-01-01

Effects of hydrologic variability on reservoir biogeochemistry are relatively unknown, particularly for less studied metals like vanadium (V). Further, few studies have investigated the fate and effects of sediment-associated V to aquatic organisms in hydrologically variable systems. Our primary objective was to assess effects of hydrologic manipulation on speciation and toxicity of V (range: 635 to 1620 mg kg- 1) and other metals to Hyalella azteca and Daphnia magna. Sediments were collected from a reservoir located in a former mining area and microcosm experiments were conducted to emulate 7-day drying and inundation periods. Despite high sediment concentrations, V bioavailability remained low with no significant effects to organism survival, growth, or reproduction. The lack of V toxicity was attributed to reduced speciation (III, IV), non-labile complexation, and sorption to Al/Fe/Mn-oxyhydroxides. Zinc (Zn) increased in surface and porewater with inundation, for some sediments exceeding the U.S. EPA threshold for chronic toxicity. While no effects of Zn to organism survival or growth were observed, Zn body concentrations were negatively correlated with H. azteca growth. Results from this study indicate that V bioavailability and environmental risk is dependent on V-speciation, and V is less influenced by hydrologic variability than more labile metals such as Zn.

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.

Voltammetric investigation of the distribution of hydroxo-, chloro-, edta and carbohydrate complexes of lead, chromium, zinc, cadmium and copper: Potential application to metal speciation studies in brewery wastewater

Directory of Open Access Journals (Sweden)

J. Catherine Ngila

2005-06-01

Full Text Available This paper reports results on complex formation reactions between OH-, Cl-, EDTA and carbohydrate ligands with Pb2+ ions at various [LT]:[MT] ratios and at different pH values (1.5-13.0. Differential pulse anodic stripping voltammetry (DPASV employing an ex situ plated thin mercury film electrode (TMFE was used to measure the shifts in peak potentials. Formation of simple, polyligand as well as mixed ligand complexes are reported. The reactions between the Pb(II and the carbohydrate ligands showed pronounced pH dependency on metal forms compared to reactions with simple inorganic ions such as chloride. Modeling of the experimental data obtained with the DPASV method was done using computer software (3D-VISE. The calculated complex formation curves (CCFC based on mass balance equations were fitted to the experimental complex formation curves (ECFC and the goodness of the fit evaluated (RSD < 5%. These studies were applied to Pb, Cr, Zn, Cd and Cu speciation in brewery wastewater in which differences between total metal determined by flame atomic absorption spectrometry (FAAS after acid digestion and labile fraction determined by DPASV were used to estimate the percentage of non-labile fraction (mainly metal-organic complexes. Up to 90% of the metal was found to exist as the “inert” fraction, implying that the effluent system from the brewery industry poses minimal health risks to the environment with regard to toxic forms of the metals as the organically bound metal forms are generally known to have low toxicity compared to the aquo or labile metal forms.

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.

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

Science.gov (United States)

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

2011-09-01

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

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

Energy Technology Data Exchange (ETDEWEB)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

2017-06-01

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth’s history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES) spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes—many containing organic ligands—we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H₂S_(aq)] < 11 µM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO₃, MoO_xS_4-x^2- (intermediate thiomolybdates), and [MoO_x(cat)_4-x]^2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS₄^2- (tetrathiomolybdate).

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)

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)

Speciation of mercury in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Jia Xiaoyu; Han Yi; Liu Xinli; Duan Taicheng; Chen Hangting

2011-01-01

The dispersive liquid-liquid microextraction (DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of mercury in water samples was described. Firstly methylmercury (MeHg + ) and mercury (Hg 2+ ) were complexed with sodium diethyldithiocarbamate, and then the complexes were extracted into carbon tetrachloride by using DLLME. Under the optimized conditions, the enrichment factors of 138 and 350 for MeHg + and Hg 2+ were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL -1 for MeHg + and 0.0014 ng mL -1 for Hg 2+ , respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL -1 MeHg + and Hg 2+ were 6.9% and 4.4%, respectively. Standard reference material of seawater (GBW(E)080042) was analyzed to verify the accuracy of the method and the results were in good agreement with the certified values. Finally, the developed method was successfully applied for the speciation of mercury in three environmental water samples.

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...

Role of uranium speciation on its bioaccumulation, transfer and toxicity in plants. Application to phyto-remediation

International Nuclear Information System (INIS)

Laurette, J.

2011-01-01

Uranium is both a radiological and a chemical toxic, which naturally occurs in the environment as a trace element. Metal accumulation and distribution in plants is modulated by speciation. The aim of this PhD work was thus to assay uranium accumulation, intra planta repartition and toxicity according to its speciation in solution. Acquired knowledge will be applied in phyto-remediation technologies. We exposed three plant species (sunflower, oilseed rape and wheat) to a panel of hydroponic media containing one or two predominant uranium chemical forms. After exposition in these various contaminated media, we evaluated uranium content in plant organs by ICP-MS. In order to investigate uranium repartition and localization at organ/tissue and cellular scales, we carried out four complementary imaging techniques. The uranium repartition within soluble and membrane fractions in roots and shoot was assayed after fractionation and separation through a chromatography column. In parallel, we used X-ray absorption spectroscopy to determine the molecular-level structure of chemical species formed by uranium in exposure media and plant samples. Finally, we explored toxic effects of uranium on plant growth and metabolism. Our results revealed three schema of accumulation according to the uranium speciation in the exposure medium: when exposed to UO 2 2+ free ion, root accumulation is high, but uranium transfer to the shoots is limited. Uranium is immobilized by adsorption on root surface and precipitation on root cell walls, associated with phosphorus and calcium. The existence of uranium-binding proteins is also suggested. When complexed with phosphate, root accumulation is considerably reduced and translocation becomes negligible. Uranium is precipitated as described above. Conversely, complexation with carbonate or citrate reduces root accumulation but drastically increases translocation to the shoots. If some uranyl phosphate precipitates are still found in root and shoot

Joint stability characteristics of the ankle complex in female athletes with histories of lateral ankle sprain, part II: clinical experience using arthrometric measurement.

Science.gov (United States)

Kovaleski, John E; Heitman, Robert J; Gurchiek, Larry R; Hollis, J M; Liu, Wei; Pearsall, Albert W

2014-01-01

This is part II of a 2-part series discussing stability characteristics of the ankle complex. In part I, we used a cadaver model to examine the effects of sectioning the lateral ankle ligaments on anterior and inversion motion and stiffness of the ankle complex. In part II, we wanted to build on and apply these findings to the clinical assessment of ankle-complex motion and stiffness in a group of athletes with a history of unilateral ankle sprain. To examine ankle-complex motion and stiffness in a group of athletes with reported history of lateral ankle sprain. Cross-sectional study. University research laboratory. Twenty-five female college athletes (age = 19.4 ± 1.4 years, height = 170.2 ± 7.4 cm, mass = 67.3 ± 10.0 kg) with histories of unilateral ankle sprain. All ankles underwent loading with an ankle arthrometer. Ankles were tested bilaterally. The dependent variables were anterior displacement, anterior end-range stiffness, inversion rotation, and inversion end-range stiffness. Anterior displacement of the ankle complex did not differ between the uninjured and sprained ankles (P = .37), whereas ankle-complex rotation was greater for the sprained ankles (P = .03). The sprained ankles had less anterior and inversion end-range stiffness than the uninjured ankles (P ankle-complex laxity and end-range stiffness were detected in ankles with histories of sprain. These results indicate the presence of altered mechanical characteristics in the soft tissues of the sprained ankles.

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.

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.

Comparison of two experimental speciation methods with a theoretical approach to monitor free and labile Cd fractions in soil solutions

International Nuclear Information System (INIS)

Parat, C.; Cornu, J.-Y.; Schneider, A.; Authier, L.; Sapin-Didier, V.; Denaix, L.; Potin-Gautier, M.

2009-01-01

This work focused on the suitability of two techniques to monitor cadmium speciation in soil solutions collected during a 7-day incubation of a contaminated soil. Anodic stripping voltammetry (ASV) and ion exchange were performed on soil solutions collected daily and results were compared with calculations obtained with the speciation software Visual MINTEQ. The electrochemically labile Cd fraction was greater than the exchange-estimated free Cd fraction during the first 6 days, after which it decreased sharply during the last 2 days to reach values close to the exchange-estimated free Cd fraction. Further investigations showed that the increase in pH was mainly responsible for the reduction. However, calculations performed with Visual MINTEQ software clearly demonstrated that a change in the nature of organic matter and/or its complexing capacity also needed to be taken into consideration.

The evolutionary history of bears is characterized by gene flow across species

Science.gov (United States)

Kumar, Vikas; Lammers, Fritjof; Bidon, Tobias; Pfenninger, Markus; Kolter, Lydia; Nilsson, Maria A.; Janke, Axel

2017-01-01

Bears are iconic mammals with a complex evolutionary history. Natural bear hybrids and studies of few nuclear genes indicate that gene flow among bears may be more common than expected and not limited to polar and brown bears. Here we present a genome analysis of the bear family with representatives of all living species. Phylogenomic analyses of 869 mega base pairs divided into 18,621 genome fragments yielded a well-resolved coalescent species tree despite signals for extensive gene flow across species. However, genome analyses using different statistical methods show that gene flow is not limited to closely related species pairs. Strong ancestral gene flow between the Asiatic black bear and the ancestor to polar, brown and American black bear explains uncertainties in reconstructing the bear phylogeny. Gene flow across the bear clade may be mediated by intermediate species such as the geographically wide-spread brown bears leading to large amounts of phylogenetic conflict. Genome-scale analyses lead to a more complete understanding of complex evolutionary processes. Evidence for extensive inter-specific gene flow, found also in other animal species, necessitates shifting the attention from speciation processes achieving genome-wide reproductive isolation to the selective processes that maintain species divergence in the face of gene flow. PMID:28422140

The evolutionary history of bears is characterized by gene flow across species.

Science.gov (United States)

Kumar, Vikas; Lammers, Fritjof; Bidon, Tobias; Pfenninger, Markus; Kolter, Lydia; Nilsson, Maria A; Janke, Axel

2017-04-19

Bears are iconic mammals with a complex evolutionary history. Natural bear hybrids and studies of few nuclear genes indicate that gene flow among bears may be more common than expected and not limited to polar and brown bears. Here we present a genome analysis of the bear family with representatives of all living species. Phylogenomic analyses of 869 mega base pairs divided into 18,621 genome fragments yielded a well-resolved coalescent species tree despite signals for extensive gene flow across species. However, genome analyses using different statistical methods show that gene flow is not limited to closely related species pairs. Strong ancestral gene flow between the Asiatic black bear and the ancestor to polar, brown and American black bear explains uncertainties in reconstructing the bear phylogeny. Gene flow across the bear clade may be mediated by intermediate species such as the geographically wide-spread brown bears leading to large amounts of phylogenetic conflict. Genome-scale analyses lead to a more complete understanding of complex evolutionary processes. Evidence for extensive inter-specific gene flow, found also in other animal species, necessitates shifting the attention from speciation processes achieving genome-wide reproductive isolation to the selective processes that maintain species divergence in the face of gene flow.

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...

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.

Asymmetry and polymorphism of hybrid male sterility during the early stages of speciation in house mice.

Science.gov (United States)

Good, Jeffrey M; Handel, Mary Ann; Nachman, Michael W

2008-01-01

House mice offer a powerful system for dissecting the genetic basis of phenotypes that isolate species in the early stages of speciation. We used a series of reciprocal crosses between wild-derived strains of Mus musculus and M. domesticus to examine F(1) hybrid male sterility, one of the primary phenotypes thought to isolate these species. We report four main results. First, we found significantly smaller testes and fewer sperm in hybrid male progeny of most crosses. Second, in some crosses hybrid male sterility was asymmetric and depended on the species origin of the X chromosome. These observations confirm and extend previous findings, underscoring the central role that the M. musculus X chromosome plays in reproductive isolation. Third, comparisons among reciprocal crosses revealed polymorphism at one or more hybrid incompatibilities within M. musculus. Fourth, the spermatogenic phenotype of this polymorphic interaction appears distinct from previously described hybrid incompatibilities between these species. These data build on previous studies of speciation in house mice and show that the genetic basis of hybrid male sterility is fairly complex, even at this early stage of divergence.

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)

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.

The underlying mechanisms of genetic innovation and speciation in the family Corynebacteriaceae: A phylogenomics approach.

Science.gov (United States)

Zhi, Xiao-Yang; Jiang, Zhao; Yang, Ling-Ling; Huang, Ying

2017-02-01

The pangenome of a bacterial species population is formed by genetic reduction and genetic expansion over the long course of evolution. Gene loss is a pervasive source of genetic reduction, and (exogenous and endogenous) gene gain is the main driver of genetic expansion. To understand the genetic innovation and speciation of the family Corynebacteriaceae, which cause a wide range of serious infections in humans and animals, we analyzed the pangenome of this family, and reconstructed its phylogeny using a phylogenomics approach. Genetic variations have occurred throughout the whole evolutionary history of the Corynebacteriaceae. Gene loss has been the primary force causing genetic changes, not only in terms of the number of protein families affected, but also because of its continuity on the time series. The variation in metabolism caused by these genetic changes mainly occurred for membrane transporters, two-component systems, and metabolism related to amino acids and carbohydrates. Interestingly, horizontal gene transfer (HGT) not only caused changes related to pathogenicity, but also triggered the acquisition of antimicrobial resistance. The Darwinian theory of evolution did not adequately explain the effects of dispersive HGT and/or gene loss in the evolution of the Corynebacteriaceae. These findings provide new insight into the evolution and speciation of Corynebacteriaceae and advance our understanding of the genetic innovation in microbial populations. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Simultaneous Speciation of Arsenic, Selenium, and Chromium by HPLC-ICP-MS

Science.gov (United States)

Wolf, Ruth E.; Morman, Suzette A.; Morrison, Jean M.; Lamothe, Paul J.

2008-01-01

An adaptation of an analytical method developed for chromium speciation has been utilized for the simultaneous determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) species using high performance liquid chromatography (HPLC) separation with ICP-MS detection. Reduction of interferences for the determination of As, Se, and Cr by ICP-MS is a major consideration for this method. Toward this end, a Dynamic Reaction Cell (DRC) ICP-MS system was used to detect the species eluted from the chromatographic column. A variety of reaction cell gases and conditions may be utilized, and the advantages and limitations of the gases tested to date will be presented and discussed. The separation and detection of the As, Se, and Cr species of interest can be achieved using the same chromatographic conditions in less than 2 minutes by complexing the Cr(III) with EDTA prior to injection on the HPLC column. Practical aspects of simultaneous speciation analysis will be presented and discussed, including issues with HPLC sample vial contamination, standard and sample contamination, species stability, and considerations regarding sample collection and preservation methods. The results of testing to determine the method's robustness to common concomitant element and anion effects will also be discussed. Finally, results will be presented using the method for the analysis of a variety of environmental and geological samples including waters, soil leachates and simulated bio-fluid leachates.

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.

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

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.

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.

Neutral Theory: From Complex Population History to Natural Selection and Sociocultural Phenomena in Human Populations.

Science.gov (United States)

Austerlitz, Frédéric; Heyer, Evelyne

2018-06-01

Here, we present a synthetic view on how Kimura's Neutral theory has helped us gaining insight on the different evolutionary forces that shape human evolution. We put this perspective in the frame of recent emerging challenges: the use of whole genome data for reconstructing population histories, natural selection on complex polygenic traits, and integrating cultural processes in human evolution.

Larval Performance in the Context of Ecological Diversification and Speciation in Lycaeides Butterflies

Directory of Open Access Journals (Sweden)

Cynthia F. Scholl

2012-01-01

Full Text Available The role of ecology in diversification has been widely investigated, though few groups have been studied in enough detail to allow comparisons of different ecological traits that potentially contribute to reproductive isolation. We investigated larval performance within a species complex of Lycaeides butterflies. Caterpillars from seven populations were reared on five host plants, asking if host-specific, adaptive larval traits exist. We found large differences in performance across plants and fewer differences among populations. The patterns of performance are complex and suggest both conserved traits (i.e., plant effects across populations and more recent dynamics of local adaptation, in particular for L. melissa that has colonized an exotic host. We did not find a relationship between oviposition preference and larval performance, suggesting that preference did not evolve to match performance. Finally, we put larval performance within the context of several other traits that might contribute to ecologically based reproductive isolation in the Lycaeides complex. This larger context, involving multiple ecological and behavioral traits, highlights the complexity of ecological diversification and emphasizes the need for detailed studies on the strength of putative barriers to gene flow in order to fully understand the process of ecological speciation.

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

Science.gov (United States)

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

2008-06-01

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

Intelligent Design and Earth History

Science.gov (United States)

Elders, W. A.

2001-05-01

Intelligent Design (ID), the idea that the Earth's biota was intelligently designed and created, is not a new species recently evolved by allopatric speciation at the fringes of the creationist gene pool. In spite of its new veneer of sophistication, ID is a variant of an already extant species of religious polemics. In the western world, arguments about causative relationships between the complexity of nature and the supernatural can be traced from the fifth century St. Augustine, to the eighteenth century David Hume and the nineteenth century William Paley. Along this descent tree some argued from the existence of supernatural agencies to the creation of nature with its complexities, while others argued from the complexities of nature to the existence of supernatural agencies. Today, Phillip Johnson promotes ID by attacking evolution rather than by presenting evidence for ID. He argues that the evidence for macroevolution is either absent, misinterpreted or fraudulent. His "Wedge Strategy" attempts to separate his "objective science" from the "philosophical mechanistic naturalism" which he posits is responsible for the survival of Darwinism. To make his appeal as wide as possible he tries not to offend anyone (except evolutionists) by deliberately avoiding discussion of biblical literalism or the age of the Earth. Although in 1859 Darwin admitted that the geological evidence was "the most obvious and gravest objection which can be urged against my theory", subsequently geological evidence has become one of the chief supports of his theory. However, the fossil record is now seen to be not simply one of slow gradual descent with modification. Rates of divergence and disappearance of organisms have varied enormously through time. Repeated mass extinctions indicate a strong element of contingency in evolution. Accepting the postulate of an intelligent designer also requires the postulate of an intelligent destroyer. Darwin hinted at this when he referred to, "The

Diversity and endemism in deglaciated areas: ploidy, relative genome size and niche differentiation in the Galium pusillum complex (Rubiaceae) in Northern and Central Europe

Science.gov (United States)

Kolář, Filip; Lučanová, Magdalena; Vít, Petr; Urfus, Tomáš; Chrtek, Jindřich; Fér, Tomáš; Ehrendorfer, Friedrich; Suda, Jan

2013-01-01

Background and Aims Plants endemic to areas covered by ice sheets during the last glaciation represent paradigmatic examples of rapid speciation in changing environments, yet very few systems outside the harsh arctic zone have been comprehensively investigated so far. The Galium pusillum aggregate (Rubiaceae) is a challenging species complex that exhibits a marked differentiation in boreal parts of Northern Europe. As a first step towards understanding its evolutionary history in deglaciated regions, this study assesses cytological variation and ecological preferences of the northern endemics and compares the results with corresponding data for species occurring in neighbouring unglaciated parts of Central and Western Europe. Methods DNA flow cytometry was used together with confirmatory chromosome counts to determine ploidy levels and relative genome sizes in 1158 individuals from 181 populations. A formalized analysis of habitat preferences was applied to explore niche differentiation among species and ploidy levels. Key Results The G. pusillum complex evolved at diploid and tetraploid levels in Northern Europe, in contrast to the high-polyploid evolution of most other northern endemics. A high level of eco-geographic segregation was observed between different species (particularly along gradients of soil pH and competition) which is unusual for plants in deglaciated areas and most probably contributes to maintaining species integrity. Relative monoploid DNA contents of the species from previously glaciated regions were significantly lower than those of their counterparts from mostly unglaciated Central Europe, suggesting independent evolutionary histories. Conclusions The aggregate of G. pusillum in Northern Europe represents an exceptional case with a geographically vicariant and ecologically distinct diploid/tetraploid species endemic to formerly glaciated areas. The high level of interspecific differentiation substantially widens our perception of the

Pronounced fixation, strong population differentiation and complex population history in the Canary Islands blue tit subspecies complex.

Science.gov (United States)

Hansson, Bengt; Ljungqvist, Marcus; Illera, Juan-Carlos; Kvist, Laura

2014-01-01

Evolutionary molecular studies of island radiations may lead to insights in the role of vicariance, founder events, population size and drift in the processes of population differentiation. We evaluate the degree of population genetic differentiation and fixation of the Canary Islands blue tit subspecies complex using microsatellite markers and aim to get insights in the population history using coalescence based methods. The Canary Island populations were strongly genetically differentiated and had reduced diversity with pronounced fixation including many private alleles. In population structure models, the relationship between the central island populations (La Gomera, Tenerife and Gran Canaria) and El Hierro was difficult to disentangle whereas the two European populations showed consistent clustering, the two eastern islands (Fuerteventura and Lanzarote) and Morocco weak clustering, and La Palma a consistent unique lineage. Coalescence based models suggested that the European mainland forms an outgroup to the Afrocanarian population, a split between the western island group (La Palma and El Hierro) and the central island group, and recent splits between the three central islands, and between the two eastern islands and Morocco, respectively. It is clear that strong genetic drift and low level of concurrent gene flow among populations have shaped complex allelic patterns of fixation and skewed frequencies over the archipelago. However, understanding the population history remains challenging; in particular, the pattern of extreme divergence with low genetic diversity and yet unique genetic material in the Canary Island system requires an explanation. A potential scenario is population contractions of a historically large and genetically variable Afrocanarian population, with vicariance and drift following in the wake. The suggestion from sequence-based analyses of a Pleistocene extinction of a substantial part of North Africa and a Pleistocene/Holocene eastward

Pronounced fixation, strong population differentiation and complex population history in the Canary Islands blue tit subspecies complex.

Directory of Open Access Journals (Sweden)

Bengt Hansson

Full Text Available Evolutionary molecular studies of island radiations may lead to insights in the role of vicariance, founder events, population size and drift in the processes of population differentiation. We evaluate the degree of population genetic differentiation and fixation of the Canary Islands blue tit subspecies complex using microsatellite markers and aim to get insights in the population history using coalescence based methods. The Canary Island populations were strongly genetically differentiated and had reduced diversity with pronounced fixation including many private alleles. In population structure models, the relationship between the central island populations (La Gomera, Tenerife and Gran Canaria and El Hierro was difficult to disentangle whereas the two European populations showed consistent clustering, the two eastern islands (Fuerteventura and Lanzarote and Morocco weak clustering, and La Palma a consistent unique lineage. Coalescence based models suggested that the European mainland forms an outgroup to the Afrocanarian population, a split between the western island group (La Palma and El Hierro and the central island group, and recent splits between the three central islands, and between the two eastern islands and Morocco, respectively. It is clear that strong genetic drift and low level of concurrent gene flow among populations have shaped complex allelic patterns of fixation and skewed frequencies over the archipelago. However, understanding the population history remains challenging; in particular, the pattern of extreme divergence with low genetic diversity and yet unique genetic material in the Canary Island system requires an explanation. A potential scenario is population contractions of a historically large and genetically variable Afrocanarian population, with vicariance and drift following in the wake. The suggestion from sequence-based analyses of a Pleistocene extinction of a substantial part of North Africa and a Pleistocene

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)

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

Science.gov (United States)

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

2011-01-01

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

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)

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

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...

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

Aquatic Humic Substances: Relationship Between Origin and Complexing Capacity.

Science.gov (United States)

González-Guadarrama, María de Jesús; Armienta-Hernández, Ma Aurora; Rosa, André H

2018-05-01

Aiming to determine the relationship between source and complexing capacity, humic substances obtained from three sites (Sorocaba and Itapanhau Brasilian rivers, and Xochimilco Lake in Mexico) were studied. Copper, manganese, zinc and arsenic complexing capacity were determined for the three substances under various pH conditions. Results showed similar complexing capacity for the three elements depending on the chemistry of each one and on the physico-chemical conditions. Speciation diagrams showed that these conditions affect both, the humic substances, and the transition metals and arsenic.

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

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.

Transgenic Drosophila simulans strains prove the identity of the speciation gene Lethal hybrid rescue.

Science.gov (United States)

Prigent, Stéphane R; Matsubayashi, Hiroshi; Yamamoto, Masa-Toshi

2009-10-01

Speciation genes are responsible for genetic incompatibilities in hybrids of incipient species and therefore participate in reproductive isolation leading to complete speciation. Hybrid males between Drosophila melanogaster females and D. simulans males die at late larval or prepupal stages due to a failure in chromosome condensation during mitosis. However a mutant male of D. simulans, named Lethal hybrid rescue (Lhr), produces viable hybrid males when crossed to females of D. melanogaster. Recently the Lhr gene has been proposed as corresponding to the CG18468 gene in D. melanogaster. However this identification relied on sequence characteristics more than on a precise mapping and the use of the GAL4/UAS system to drive the transgene in D. melanogaster might have increased the complexity of interaction. Thus here we propose an independent identification of the Lhr gene based on a more precise mapping and transgenic experiments in D. simulans. We have mapped the Lhr gene by using Single Nucleotide Polymorphisms (SNPs) and identified within the candidate region the gene homologous to CG18468 as the Lhr gene as it was previously reported. Transgenic experiments in D. simulans with the native promoter of CG18468 prove that it is the Lhr gene of D. simulans by inducing the lethality of the hybrid males.

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

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.

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.

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

Molecular evidence of cryptic speciation in the "cosmopolitan" excavating sponge Cliona celata (Porifera, Clionaidae).

Science.gov (United States)

Xavier, J R; Rachello-Dolmen, P G; Parra-Velandia, F; Schönberg, C H L; Breeuwer, J A J; van Soest, R W M

2010-07-01

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 important species-the excavating sponge Cliona celata (Clionaidae, Hadromerida). In the Northeast Atlantic and Mediterranean C. celata displays a discontinuous distribution of its putative growth stages (boring, encrusting, and massive) leading us to investigate its specific status. Phylogenetic reconstructions of mitochondrial (COI, Atp8) and nuclear (28S) gene fragments revealed levels of genetic diversity and divergence compatible with interspecific relationships. We therefore demonstrate C. celata as constituting a species complex comprised of at least four morphologically indistinct species, each showing a far more restricted distribution: two species on the Atlantic European coasts and two on the Mediterranean and adjacent Atlantic coasts (Macaronesian islands). Our results provide further confirmation that the different morphotypes do indeed constitute either growth stages or ecologically adapted phenotypes as boring and massive forms were found in two of the four uncovered species. We additionally provide an overview of the cases of cryptic speciation which have been reported to date within the Porifera, and highlight how taxonomic crypsis may confound scientific interpretation and hamper biotechnological advancement. Our work together with previous studies suggests that overconservative systematic traditions but also morphological stasis have led to genetic complexity going undetected and that a DNA-assisted taxonomy may play a key role in uncovering the hidden diversity in this taxonomic group. Copyright 2010 Elsevier Inc. All rights reserved.

On the Bur Gheluai H5 chondrite and other meteorites with complex exposure histories

Science.gov (United States)

Vogt, S. K.; Aylmer, D.; Herzog, G. F.; Wieler, R.; Signer, P.; Pellas, P.; Fieni, C.; Tuniz, C.; Jull, A. J. T.; Fink, D.

1993-01-01

Isotopic concentrations and track densities measured in 13 samples of the Bur Gheluai meteorite fall are presented. Experimental methods are described and results are presented for isotopic ratios of noble gases and cosmogenic radionuclide contents. Evidence for complex irradiation is discussed and a model for two-stage exposure histories is presented. The duration of each irradiation stage and possible effects on isotope production rates are considered. Explanations are suggested for the discrepant Ne production rates.

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.

Characterization of iron speciation in urban and rural single particles using XANES spectroscopy and micro X-ray fluorescence measurements: investigating the relationship between speciation and fractional iron solubility

OpenAIRE

Oakes, M.; Weber, R. J.; Lai, B.; Russell, A.; Ingall, E. D.

2012-01-01

Soluble iron in fine atmospheric particles has been identified as a public health concern by participating in reactions that generate reactive oxygen species (ROS). The mineralogy and oxidation state (speciation) of iron have been shown to influence fractional iron solubility (soluble iron/total iron). In this study, iron speciation was determined in single particles at urban and rural sites in Georgia USA using synchrotron-based techniques, such as X-ray Absorption Near-Edge Structure (XANES...

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.

Reconstruction of phylogenetic relationships in a highly reticulate group with deep coalescence and recent speciation (Hieracium, Asteraceae).

Science.gov (United States)

Krak, K; Caklová, P; Chrtek, J; Fehrer, J

2013-02-01

Phylogeny reconstruction based on multiple unlinked markers is often hampered by incongruent gene trees, especially in closely related species complexes with high degrees of hybridization and polyploidy. To investigate the particular strengths and limitations of chloroplast DNA (cpDNA), low-copy nuclear and multicopy nuclear markers for elucidating the evolutionary history of such groups, we focus on Hieracium s.str., a predominantly apomictic genus combining the above-mentioned features. Sequences of the trnV-ndhC and trnT-trnL intergenic spacers were combined for phylogenetic analyses of cpDNA. Part of the highly variable gene for squalene synthase (sqs) was applied as a low-copy nuclear marker. Both gene trees were compared with previous results based on the multicopy external transcribed spacer (ETS) of the nuclear ribosomal DNA. The power of the different markers to detect hybridization varied, but they largely agreed on particular hybrid and allopolyploid origins. The same crown groups of species were recognizable in each dataset, but basal relationships were strongly incongruent among cpDNA, sqs and ETS trees. The ETS tree was considered as the best approximation of the species tree. Both cpDNA and sqs trees showed basal polytomies as well as merging or splitting of species groups of non-hybrid taxa. These patterns can be best explained by a rapid diversification of the genus with ancestral polymorphism and incomplete lineage sorting. A hypothetical scenario of Hieracium speciation based on all available (including non-molecular) evidence is depicted. Incorporation of seemingly contradictory information helped to better understand species origins and evolutionary patterns in this notoriously difficult agamic complex.

Speciation of mercury in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Jia Xiaoyu; Han Yi; Liu Xinli [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Duan Taicheng, E-mail: tcduan@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China); Chen Hangting, E-mail: htchen@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China)

2011-01-15

The dispersive liquid-liquid microextraction (DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of mercury in water samples was described. Firstly methylmercury (MeHg{sup +}) and mercury (Hg{sup 2+}) were complexed with sodium diethyldithiocarbamate, and then the complexes were extracted into carbon tetrachloride by using DLLME. Under the optimized conditions, the enrichment factors of 138 and 350 for MeHg{sup +} and Hg{sup 2+} were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL{sup -1} for MeHg{sup +} and 0.0014 ng mL{sup -1} for Hg{sup 2+}, respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL{sup -1} MeHg{sup +} and Hg{sup 2+} were 6.9% and 4.4%, respectively. Standard reference material of seawater (GBW(E)080042) was analyzed to verify the accuracy of the method and the results were in good agreement with the certified values. Finally, the developed method was successfully applied for the speciation of mercury in three environmental water samples.

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

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.

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.

Medical history and the onset of complex regional pain syndrome (CRPS).

Science.gov (United States)

de Mos, M; Huygen, F J P M; Dieleman, J P; Koopman, J S H A; Stricker, B H Ch; Sturkenboom, M C J M

2008-10-15

Knowledge concerning the medical history prior to the onset of complex regional pain syndrome (CRPS) might provide insight into its risk factors and potential underlying disease mechanisms. To evaluate prior to CRPS medical conditions, a case-control study was conducted in the Integrated Primary Care Information (IPCI) project, a general practice (GP) database in the Netherlands. CRPS patients were identified from the records and validated through examination by the investigator (IASP criteria) or through specialist confirmation. Cases were matched to controls on age, gender and injury type. All diagnoses prior to the index date were assessed by manual review of the medical records. Some pre-specified medical conditions were studied for their association with CRPS, whereas all other diagnoses, grouped by pathogenesis, were tested in a hypothesis-generating approach. Of the identified 259 CRPS patients, 186 cases (697 controls) were included, based on validation by the investigator during a visit (102 of 134 visited patients) or on specialist confirmation (84 of 125 unvisited patients). A medical history of migraine (OR: 2.43, 95% CI: 1.18-5.02) and osteoporosis (OR: 2.44, 95% CI: 1.17-5.14) was associated with CRPS. In a recent history (1-year before CRPS), cases had more menstrual cycle-related problems (OR: 2.60, 95% CI: 1.16-5.83) and neuropathies (OR: 5.7; 95% CI: 1.8-18.7). In a sensitivity analysis, including only visited cases, asthma (OR: 3.0; 95% CI: 1.3-6.9) and CRPS were related. Psychological factors were not associated with CRPS onset. Because of the hypothesis-generating character of this study, the findings should be confirmed by other studies.

STABILITY OF BINARY COMPLEXES OF L-ASPARTIC ACID IN ...

African Journals Online (AJOL)

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KEY WORDS: Binary complexes, Stability constants, Aspartic acid, Speciation, Dioxan. INTRODUCTION. 1,4-Dioxan (Dox) is ... It is miscible with water, oils, and most organic solvents, including aromatic .... of mineral acid in metal ion and ligand solutions was determined using the Gran plot method. [28, 29]. To assess the ...

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.

Speciation of High-Pressure Carbon-Saturated COH Fluids at Buffered fO2 Conditions: An Experimental Approach

Science.gov (United States)

Tumiati, S.; Tiraboschi, C.; Recchia, S.; Poli, S.

2014-12-01

evolved gases are then convoyed to a quadrupole mass spectrometer through a heated line to avoid the condensation of water. Our results suggest that fluid speciation can diverge considerably compared to the thermodynamic model depending on the experimental strategies adopted and on the presence of solutes in complex COH systems.

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

Organic complexing agents in low and medium level radioactive waste

International Nuclear Information System (INIS)

Allard, B.; Persson, G.

1985-11-01

Low and medium level radioactive wastes will contain various organic agents, such as ion exchange resins (mainly in the operational wastes), plastics and cellulose (mainly in the reprocessing wastes and in the decommissioning wastes) and bitumen (mainly in the reprocessing wastes). The degradation of these organics will lead to the formation of complexing agents that possibly could affect the release of radionuclides from an underground repository and the subsequent transport of these nuclides. The solution chemistry of the actinides may be totally dominated by the presence of such organic degradation products within the repository. However, hydrolysis and formation of carbonates (and possibly humates) will most likely dominate solubility and speciation outside the immediate vicinity of the repository. The minor quantities of strong complexing agents (in the reprocessing waste), notably aminopolycarboxylic acids (EDTA, DTPA) and possibly organic phosphates (DBP) could significantly affect speciation and sorption behaviour of primarily the trivalent actinides even outside the repository. (author)

Complex regional pain syndromes (CRPS type 1 validating case histories

Directory of Open Access Journals (Sweden)

P. Berger

2003-01-01

Full Text Available The treatment of patients with complex regional pain syndrome (CRPS type 1 is challenging and unpredictable as the condition presents with vascular and neuropathic symptoms after nil or even minor injury to a peripheral nerve. The condition is one of a pain and motor dysfunction. The pathophysiology is not well understood and the relief of symptoms may change from being sympathetically mediated to sympathetically independent during  the course of the disease. At any stage physiotherapy has been advocated as the corner stone and most important aspect of treatment in the rehabilitation of these individuals but unfortunately it has been difficult to execute when pain is exacerbated due to allodynia (unbearable to touch or move and hyperalgesia. Best results have been obtained if the patients are recognised and treated in the early or acute phase and it has been found that through careful assessment and analysis these patients can be recognised by previous events that have occurred in their initial case history. The treatment in the acute stage with physiotherapy modalities such as electrical stimulation and acupuncture will produce an early cessation of the symptoms and prevention of the disease developing into the fully blown CRPS type 1 with irreversible and possibly atrophic consequences. Case histories have been presented that illustrate these important aspects and demonstrate  the value of early and the appropriate physiotherapy that may be more successful than other pharmacological and physical interventions in this disease.

Interactions between hydrated cement paste and organic acids: Thermodynamic data and speciation modeling

Energy Technology Data Exchange (ETDEWEB)

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr [MINES ParisTech, PSL Research University, Centre de Géosciences, 35 Rue St-Honoré, 77305 Fontainebleau Cedex (France); Bertron, Alexandra; Larreur-Cayol, Steeves; Escadeillas, Gilles [University of Toulouse, UPS/INSA/LMDC, 135 Av. de Rangueil, 31077 Toulouse Cedex 04 (France)

2015-03-15

Interactions of short-chain organic acids with hydrated cement phases affect structure durability in the agro-food and nuclear waste industries but can also be used to modify cement properties. Most previous studies have been experimental, performed at fixed concentrations and pH, without quantitatively discriminating among polyacidity effects, or complexation and salt precipitation processes. This paper addresses such issues by thermodynamic equilibrium calculations for acetic, citric, oxalic, succinic acids and a simplified hydrated CEM-I. The thermodynamic constants collected from the literature allow the speciation to be modeled over a wide range of pH and concentrations. Citric and oxalic had a stronger chelating effect than acetic acid, while succinic acid was intermediate. Similarly, Ca-citrate and Ca-oxalate salts were more insoluble than Ca-acetate and Ca-succinate salts. Regarding aluminium complexation, hydroxyls, sulfates, and acid competition was highlighted. The exploration of acid mixtures showed the preponderant effect of oxalate and citrate over acetate and succinate.

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

Ternary complex formation at mineral/solution interfaces

International Nuclear Information System (INIS)

Leckie, J.O.

1995-01-01

Adsorption of trace concentrations of radionuclides and heavy metals from aqueous solution is dependent on pH, absorbent and adsorbate concentration, and speciation of the metal in solution. In particular, complexation of metal ions by organic and inorganic ligands can dramatically alter adsorption behavior compared to ligand-free systems. The presence of complexing ligands can cause the formation of ''metal like'' or ''ligand like'' ternary surface complexes depending on whether adsorption of the ternary complex increases or decreases with increasing pH, respectively. Examples of ternary surface complexes behaving ''metal like'' include uranyl-EDTA surface complexes on goethite, neptunyl-EDTA surface complexes on hematite and neptunyl-humic surface complexes on gibbsite. Examples of ''ligand like'' ternary surface complexes include uranyl-carbonato and neptunyl-carbonato surface complexes on iron oxides. The effects of complex solutions and multimineralic systems are discussed. (authors). 39 refs., 16 figs., 8 tabs

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.

Population Structure and Evolution after Speciation of the Hokkaido Salamander (Hynobius retardatus.

Directory of Open Access Journals (Sweden)

Masatoshi Matsunami

Full Text Available The Hokkaido salamander (Hynobius retardatus is endemic to Hokkaido Island, Japan, and shows intriguing flexible phenotypic plasticity and regional morphological diversity. However, to date, allozymes and partial mitochondria DNA sequences have provided only an outline of its demographic histories and the pattern of its genetic diversification. To understand the finer details of the population structure of this species and its evolution since speciation, we genotyped five regional populations by using 12 recently developed microsatellite polymorphic markers. We found a clear population structure with low gene flow among the five populations, but a close genetic relationship between the Teshio and Kitami populations. Our demographic analysis suggested that Teshio and Erimo had the largest effective population sizes among the five populations. These findings regarding the population structure and demography of H. retardatus improve our understanding of the faunal phylogeography on Hokkaido Island and also provide fundamental genetic information that will be useful for future studies.

Effects of Diet Restriction and Diet Complexity on Life History Strategies in Side-Blotched Lizards (Uta stansburiana).

Science.gov (United States)

Skinner, Heather M; Durso, Andrew M; Neuman-Lee, Lorin A; Durham, Susan L; Mueller, Sarah D; French, Susannah S

2016-11-01

Organisms must balance energy invested into self-maintenance, reproduction, and somatic growth over their lifetime. In this study, the effects of diet restriction and diet complexity on side-blotched lizards (Uta stansburiana) were analyzed. Thirty male lizards, housed in the laboratory, were fed either an ad libitum or a restricted diet for 18 days (phase 1). Individuals from both treatments were then assigned to a diet of the same quantity of food that was either simple (only crickets) or complex (crickets, cockroaches, waxworms, and mealworms) for 35 days (phase 2). We evaluated (1) how diet restriction affected life history strategies and (2) how diet complexity affected recovery from diet restriction as measured at the end of phase 2 by body mass, snout-vent length, calculated body condition score, wound healing, tail regrowth, bacterial killing ability, oxidative stress, and plasma testosterone and corticosterone concentrations. Lizards without diet restriction allocated more energy to self-maintenance (i.e., maintaining higher body condition scores, healing wounds more quickly) than lizards with diet restriction. Lizards with diet restriction had higher plasma testosterone concentrations and larger increases in snout-vent lengths than those fed ad libitum, which may reflect allocations toward reproduction and somatic growth. A complex diet resulted in better body condition and faster tail regrowth than a simple diet, suggesting that a complex diet enhanced recovery from diet restriction, although long-term life history choices remained unaltered. Finally, lizards on a complex diet consumed substantially less food while maintaining higher body condition, suggesting that key nutrients may be lacking from a simple diet. © 2017 Wiley Periodicals, Inc.

Tea-industry waste activated carbon, as a novel adsorbent, for separation, preconcentration and speciation of chromium

Energy Technology Data Exchange (ETDEWEB)

Duran, Celal, E-mail: cduran@ktu.edu.tr [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Ozdes, Duygu [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey); Gundogdu, Ali [Faculty of Engineering, Food Department of Food Engineering, 29100, Guemueshane (Turkey); Imamoglu, Mustafa [Department of Chemistry, Faculty of Arts and Sciences, Sakarya University, 54187 Sakarya (Turkey); Senturk, Hasan Basri [Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon (Turkey)

2011-02-28

Activated carbon was produced from tea-industry wastes (TIWAC) and employed as a low cost and effective solid phase material for the separation, preconcentration and speciation of chromium species without using a complexing agent, prior to determination by flame atomic absorption spectrometry (FAAS). The characterization of TIWAC was performed by utilizing several techniques such as Fourier Transform Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), and elemental analysis. The adsorption experiments were conducted in a batch adsorption technique. Under the experimental conditions, Cr(VI) adsorption amount was nearly equal to zero, however the adsorption percentage of Cr(III) was in the range of 95-100%. Therefore total chromium was determined after the reduction of Cr(VI) to Cr(III) and Cr(VI) was calculated by subtracting Cr(III) concentration from total chromium concentration. The suitable conditions for adsorption and speciation processes were evaluated in terms of pH, eluent type and volume, TIWAC concentration, adsorption and desorption contact time, etc. Adsorption capacity of TIWAC was found to be 61.0 mg g{sup -1}. The detection limit for Cr(III) was found to be 0.27 {mu}g L{sup -1} and the preconcentration factor was 50 for 200 mL of sample volume. The procedure was applied to the determination and speciation of chromium in stream, tap and sea water. Also, the proposed method was applied to total chromium preconcentration in microwave digested tobacco and dried eggplant samples with satisfactory results. The method was validated by analyzing certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) and the results were in good agreement with the certified values.

Tea-industry waste activated carbon, as a novel adsorbent, for separation, preconcentration and speciation of chromium

International Nuclear Information System (INIS)

Duran, Celal; Ozdes, Duygu; Gundogdu, Ali; Imamoglu, Mustafa; Senturk, Hasan Basri

2011-01-01

Activated carbon was produced from tea-industry wastes (TIWAC) and employed as a low cost and effective solid phase material for the separation, preconcentration and speciation of chromium species without using a complexing agent, prior to determination by flame atomic absorption spectrometry (FAAS). The characterization of TIWAC was performed by utilizing several techniques such as Fourier Transform Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), and elemental analysis. The adsorption experiments were conducted in a batch adsorption technique. Under the experimental conditions, Cr(VI) adsorption amount was nearly equal to zero, however the adsorption percentage of Cr(III) was in the range of 95-100%. Therefore total chromium was determined after the reduction of Cr(VI) to Cr(III) and Cr(VI) was calculated by subtracting Cr(III) concentration from total chromium concentration. The suitable conditions for adsorption and speciation processes were evaluated in terms of pH, eluent type and volume, TIWAC concentration, adsorption and desorption contact time, etc. Adsorption capacity of TIWAC was found to be 61.0 mg g -1 . The detection limit for Cr(III) was found to be 0.27 μg L -1 and the preconcentration factor was 50 for 200 mL of sample volume. The procedure was applied to the determination and speciation of chromium in stream, tap and sea water. Also, the proposed method was applied to total chromium preconcentration in microwave digested tobacco and dried eggplant samples with satisfactory results. The method was validated by analyzing certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) and the results were in good agreement with the certified values.

Changes in U(VI) speciation upon sorption onto montmorillonite from aqueous and organic solutions

International Nuclear Information System (INIS)

Chisholm-Brause, C.; Morris, D.E.; Eller, P.G.; Buscher, T.; Conradson, S.D.

1991-01-01

The speciation of UO 2 2+ and UO 2 2+ Tributylphosphate (TBP) mixtures has been investigated in solution and intercalated with the reference smectite clay SAz-1 using x-ray absorption, Raman, and luminescence spectroscopies. Neither aquated UO 2 2+ nor its TBP complex undergoes any detectable changes in uranium oxidation state on intercalation. Further, at the pH values employed in this work, there is no evidence for hydrolysis of the uranium species to generate dimeric or higher order uranium oligomers. However, we do find indications that the structures of the solution complexes are altered on intercalation, particularly for the UO 2 2+ /TBP system. In addition, several lines of evidence suggest that, at the loading levels used in this study, the uranyl species may be interacting with two or more spectroscopically distinguishable sites on SAz-1. 29 refs., 3 figs., 2 tabs

History of science, physics, and art: a complex approach in Brazilian syllabuses

Science.gov (United States)

Braga, Marco; Guerra, Andreia; Reis, José Claudio

2013-09-01

This paper is about new contents that can be introduced into science education. It is a description of an experience aimed at introducing a complex approach into the final grade of a Brazilian elementary school. The aim is to show the transformation of the conception of space and time from the Middle Ages with the physics of Aristotle to the 20th century, when a new conception arose with the physics of Einstein. These changes were accompanied by new visions of space and time in both physics and arts. Comparison between these two expressions of human culture is used to introduce science as a human construct inserted into history.

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.

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.

Are sympatrically speciating Midas cichlid fish special? Patterns of morphological and genetic variation in the closely related species Archocentrus centrarchus.

Science.gov (United States)

Fruciano, Carmelo; Franchini, Paolo; Raffini, Francesca; Fan, Shaohua; Meyer, Axel

2016-06-01

Established empirical cases of sympatric speciation are scarce, although there is an increasing consensus that sympatric speciation might be more common than previously thought. Midas cichlid fish are one of the few substantiated cases of sympatric speciation, and they formed repeated radiations in crater lakes. In contrast, in the same environment, such radiation patterns have not been observed in other species of cichlids and other families of fish. We analyze morphological and genetic variation in a cichlid species (Archocentrus centrarchus) that co-inhabits several crater lakes with the Midas species complex. In particular, we analyze variation in body and pharyngeal jaw shape (two ecologically important traits in sympatrically divergent Midas cichlids) and relate that to genetic variation in mitochondrial control region and microsatellites. Using these four datasets, we analyze variation between and within two Nicaraguan lakes: a crater lake where multiple Midas cichlids have been described and a lake where the source population lives. We do not observe any within-lake clustering consistent across morphological traits and genetic markers, suggesting the absence of sympatric divergence in A. centrarchus. Genetic differentiation between lakes was low and morphological divergence absent. Such morphological similarity between lakes is found not only in average morphology, but also when analyzing covariation between traits and degree of morphospace occupation. A combined analysis of the mitochondrial control region in A. centrarchus and Midas cichlids suggests that a difference between lineages in the timing of crater lake colonization cannot be invoked as an explanation for the difference in their levels of diversification. In light of our results, A. centrarchus represents the ideal candidate to study the genomic differences between these two lineages that might explain why some lineages are more likely to speciate and diverge in sympatry than others.

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.

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.

A role for a neo-sex chromosome in stickleback speciation

Science.gov (United States)

Kitano, Jun; Ross, Joseph A.; Mori, Seiichi; Kume, Manabu; Jones, Felicity C.; Chan, Yingguang F.; Absher, Devin M.; Grimwood, Jane; Schmutz, Jeremy; Myers, Richard M.; Kingsley, David M.; Peichel, Catherine L.

2009-01-01

Sexual antagonism, or conflict between the sexes, has been proposed as a driving force in both sex chromosome turnover and speciation. Although closely related species often have different sex chromosome systems, it is unknown whether sex chromosome turnover contributes to the evolution of reproductive isolation between species. In this study, we show that a newly evolved sex chromosome harbours genes that contribute to speciation in threespine stickleback fish (Gasterosteus aculeatus). We first identified a neo-sex chromosome system found only in one member of a sympatric species pair in Japan. We then performed genetic linkage mapping of male-specific traits important for reproductive isolation between the Japanese species pair. The neo-X chromosome harbours loci for male courtship display traits that contribute to behavioural isolation, while the ancestral X chromosome contains loci for both behavioural isolation and hybrid male sterility. Our work not only provides strong evidence for a large-X effect on reproductive isolation in a vertebrate system, but also provides direct evidence that a young neo-X chromosome contributes to reproductive isolation between closely related species. Our data suggest that sex chromosome turnover might play a greater role in speciation than previously appreciated. PMID:19783981

Contribution to the study of the redox reactions and the speciation of technetium in chloride and carbonate media

International Nuclear Information System (INIS)

Ben Said, K.

1999-11-01

Technetium is important as a long half-life multi-valent radioelement within the framework of the nuclear waste storage especially in underground geological sites. So, the safety studies require the knowledge of the redox and of the chemical properties of this element in order to model its geochemical behaviour in the environment. Our studies deal with the redox behaviour and the speciation of technetium in chloride and carbonate media. Similar natural systems possess redox potentials likely to reduce Tc(VII) into Tc(V), Tc(IV) and Tc(III). The question of the standard redox potential of the Tc(VII)Tc(IV) couple is settled in non complexing media where Tc(IV) exists as TcO 2 (s) but is still a matter of debate in complexing media. The formal potential of the Tc(VII)/Tc(IV couple has been determined by an indirect method in 1.0 M HCl media where Tc(IV) exists as chloride complexes. The species formed by dissolving K 2 TcCl 6 (s) in chloride media have been characterised by complementary techniques of speciation (UV-visible and Raman spectrometry, X-rays absorption spectroscopy and polarography). Two chemical formulae have been proposed for the chloride species of Tc(IV) in 1.0 M HCl media as hydrolyzed TcCl 6 2- : TcCl 5 (H 2 O) - or TcCl 4 (H 2 O) 2 . The chemical or electrochemical reduction of pertechnetate in carbonate media leads to amorphous oxides or carbonate complexes of Tc(IV) and/or of Tc(III). In carbonate media, the stability of the species under γ irradiation has been estimated by UV/VIS spectrophotometry: Tc(VII) is stable but reduced into Tc(IV) in the presence of formate when the carbonate complex of Tc(IV) is oxidised into Tc(VII). So the most mobile valency Tc(VII) seems to be the stable one in irradiated carbonate media. (author)

Evidence That Speciation of Oxovanadium Complexes Does Not Solely Account for Inhibition of Leishmania Acid Phosphatases

Science.gov (United States)

Dorsey, Benjamin M.; McLauchlan, Craig C.; Jones, Marjorie A.

2018-01-01

Leishmaniasis is an endemic disease affecting a diverse spectra of populations, with 1.6 million new cases reported each year. Current treatment options are costly and have harsh side effects. New therapeutic options that have been previously identified, but still underappreciated as potential pharmaceutical targets, are Leishmania secreted acid phosphatases (SAP). These acid phosphatases, which are reported to play a role in the survival of the parasite in the sand fly vector, and in homing to the host macrophage, are inhibited by orthovanadate and decavanadate. Here, we use L. tarentolae to further evaluate these inhibitors. Using enzyme assays, and UV-visible spectroscopy, we investigate which oxovanadium starting material (orthovanadate or decavanadate) is a better inhibitor of L. tarentolae secreted acid phosphatase activity in vitro at the same total moles of vanadium. Considering speciation and total vanadium concentration, decavanadate is a consistently better inhibitor of SAP in our conditions, especially at low substrate:inhibitor ratios. PMID:29707535

Evidence that Speciation of Oxovanadium Complexes does not Solely Account for Inhibition of Leishmania Acid Phosphatases

Science.gov (United States)

Dorsey, Benjamin M.; McLauchlan, Craig C.; Jones, Marjorie A.

2018-04-01

Leishmaniasis is an endemic disease affecting a diverse spectra of populations, with 1.6 million new cases reported each year. Current treatment options are costly and have harsh side effects. New therapeutic options that have been previously identified, but still underappreciated as potential pharmaceutical targets, are Leishmania secreted acid phosphatases (SAP). These acid phosphatases, which are reported to play a role in the survival of the parasite in the sand fly vector, and in homing to the host macrophage, are inhibited by orthovanadate and decavanadate. Here, we use L. tarentolae to further evaluate these inhibitors. Using enzyme assays, and UV-visible spectroscopy, we investigate which oxovanadium starting material (orthovanadate or decavanadate) is a better inhibitor of L. tarentolae secreted acid phosphatase activity in vitro at the same total moles of vanadium. Considering speciation and total vanadium concentration, decavanadate is a consistently better inhibitor of SAP in our conditions, especially at low substrate:inhibitor ratios.

Multi-gene phylogeny of the genus Lobaria: Evidence of species-pair and allopatric cryptic speciation in East Asia.

Science.gov (United States)

Cornejo, Carolina; Scheidegger, Christoph

2015-12-01

Accurate species delimitation has critical implications for ecological and conservation studies. The lichen genus Lobaria is widely distributed in old-growth forests. Particularly in East Asia, this genus includes many rare and poorly known taxa that are circumscribed as morpho- or chemospecies, as well as species-pairs. To critically examine the relationships between species identified via morphological and chemical criteria, phylogenetic species recognition (PSR) was applied to the genus Lobaria. Morphological and chemical patterns of 87 individuals were examined and three independent nuclear loci were sequenced. The East Asian L. meridionalis-group was additionally studied using split decomposition and haplotype network analysis. The genus Lobaria and most of its species were strongly supported statistically. Split decomposition and haplotype networks suggest complex evolutionary histories of species within the East Asian L. meridionalis-group. Phylogenetic analyses confirmed the monophyly of the genus Lobaria, including L. anomala. Within Lobaria, three major clades were found. These clades associate with different photobionts and comprise 18 known species and 5 undescribed species. Several chemical compounds were found to be neither stable nor invariant characters. Some taxa of the L. meridionalis-group appear to be monophyletic but remain as allopatric cryptic species. In three clades, this study found evidence for diversification processes between isidiate and nonisidiate specimens (species-pair). These findings are discussed in the context of evolutionary hypotheses for speciation processes. © 2015 Botanical Society of America.

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...

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

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

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.

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.

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

Science.gov (United States)

Iwai, Takahiro; Chiba, Koichi; Narukawa, Tomohiro

2016-01-01

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

History or histories of socio-economic rights?

DEFF Research Database (Denmark)

Christiansen, Christian O.

2016-01-01

The German historian Reinhart Koselleck was once described as a partisan for histories in the plural (as opposed to history in the singular). His point was that history has many different layers, logics, and temporalities and that the modernist idea of one, overarching history with one direction ......) at work in the histories and dynamics of socio-economic rights. More specifically, I propose a list of eight important variables that may help explain the dynamics of the histories of socio-economic rights - their failures as well as their successes....... (telos) – be it towards progress or decline – was inadequate for the multi-faceted geographies, rhythms and dynamics of life. In these reflections on a two-days research workshop in Paris, I argue that Koselleck’s point also applies to the field of the history of socio-economic rights. Instead of writing...... the history of socio-economic rights, I would propose thinking about the histories of socio-economic rights. There are three main reasons for this: the non-teleological histories of socioeconomic rights; the distinctiveness between different socio-economic rights; and the complexity (multiple variables...

Zimbabwean history: becoming complex | Moore | African ...

African Journals Online (AJOL)

Review of Brian Raftopoulos and Alois Mlambo, eds. Becoming Zimbabwe: A History from the Pre-Colonial Period to 2008. Harare and Johannesburg: Weaver and Jacana, 2009 pp. v-xxxiv, 260. ISBN: 978-1-77922-083-7. Full Text: EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT · DOWNLOAD FULL TEXT DOWNLOAD ...

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

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.

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.

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

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.

Cloud point extraction combined with electrothermal atomic absorption spectrometry for the speciation of antimony(III) and antimony(V) in food packaging materials

International Nuclear Information System (INIS)

Jiang Xiuming; Wen Shengping; Xiang Guoqiang

2010-01-01

A simple, sensitive method for the speciation of inorganic antimony by cloud point extraction combined with electrothermal atomic absorption spectrometry (ETAAS) is presented and evaluated. The method based on the fact that formation of a hydrophobic complex of antimony(III) with ammonium pyrrolidine dithiocarbamate (APDC) at pH 5.0 and subsequently the hydrophobic complex enter into surfactant-rich phase, whereas antimony(V) remained in aqueous solutions. Antimony(III) in surfactant-rich phase was analyzed by ETAAS after dilution by 0.2 mL nitric acid in methanol (0.1 M), and antimony(V) was calculated by subtracting antimony(III) from the total antimony after reducing antimony(V) to antimony(III) by L-cysteine. The main factors affecting the cloud point extraction, such as pH, concentration of APDC and Triton X-114, equilibrium temperature and incubation time, sample volume were investigated in detail. Under the optimum conditions, the detection limit (3σ) of the proposed method was 0.02 ng mL -1 for antimony(III), and the relative standard deviation was 7.8% (c = 1.0 ng mL -1 , n = 7). The proposed method was successfully applied to speciation of inorganic antimony in the leaching solutions of different food packaging materials with satisfactory results.

Fitness landscape complexity and the emergence of modularity in neural networks

Science.gov (United States)

Lowell, Jessica

Previous research has shown that the shape of the fitness landscape can affect the evolution of modularity. We evolved neural networks to solve different tasks with different fitness landscapes, using NEAT, a popular neuroevolution algorithm that quantifies similarity between genomes in order to divide them into species. We used this speciation mechanism as a means to examine fitness landscape complexity, and to examine connections between fitness landscape complexity and the emergence of modularity.

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

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 ...

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

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.

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.

LJUNGSKILE 1.0 A Computer Program for Investigation of Uncertainties in Chemical Speciation

International Nuclear Information System (INIS)

Ekberg, Christian; Oedegaard-Jensen, Arvid

2002-11-01

In analysing the long-term safety of nuclear waste disposal, there is a need to investigate uncertainties in chemical speciation calculations. Chemical speciation is of importance in evaluating the solubility of radionuclides, the chemical degradation of engineering materials, and chemical processes controlling groundwater composition. The uncertainties in chemical speciation may for instance be related to uncertainties in thermodynamic data, the groundwater composition, or the extrapolation to the actual temperature and ionic strength. The magnitude of such uncertainties and its implications are seldom explicitly evaluated in any detail. Commonly available chemical speciation programmes normally do not have a build-in option to include uncertainty ranges. The program developed within this project has the capability of incorporating uncertainty ranges in speciation calculations and can be used for graphical presentation of uncertainty ranges for dominant species. The program should be regarded as a starting point for assessing uncertainties in chemical speciation, since it is not yet comprehensive in its capabilities. There may be limitations in its usefulness to address various geochemical problems. The LJUNGSKILE code allows the user to select two approaches: the Monte Carlo (MC) approach and the Latin Hypercube Sampling (LHS). LHS allows to produce a satisfactory statistics with a minimum of CPU time. It is, in general, possible to do a simple theoretical speciation calculation within seconds. There are, admittedly, alternatives to LHS and there is criticism towards the uncritical use of LHS output because commonly correlation between some of the input variables exists. LHS, like MC, is not capable to take these correlations into account. Such a correlation can, i.e. exist between the pH of a solution and the partial pressure of CO 2 : higher pH solutions may absorb larger amounts of CO 2 and can reduce the CO 2 partial pressure. It is therefore of advantage to

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

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

BeerOz, a set of Matlab routines for the quantitative interpretation of spectrophotometric measurements of metal speciation in solution

Science.gov (United States)

Brugger, Joël

2007-02-01

The modelling of the speciation and mobility of metals under surface and hydrothermal conditions relies on the availability of accurate thermodynamic properties for all relevant minerals, aqueous species, gases and surface species. Spectroscopic techniques obeying the Beer-Lambert law can be used to obtain thermodynamic properties for reactions among aqueous species (e.g., ligand substitution; protonation). BeerOz is a set of Matlab routines designed to perform both qualitative and quantitative analysis of spectroscopic data following the Beer-Lambert law. BeerOz is modular and can be customised for particular experimental strategies or for simultaneous refinement of several datasets obtained using different techniques. Distribution of species calculations are performed using an implementation of the EQBRM code, which allows for customised activity coefficient calculations. BeerOz also contains routines to study the n-dimensional solution space, in order to provide realistic estimates of errors and test for the existence of multiple local minima and correlation between the different refined variables. The paper reviews the physical principles underlying the qualitative and quantitative analysis of spectroscopic data collected on aqueous speciation, in particular for studying successive ligand replacement reactions, and presents the non-linear least-squares algorithm implemented in BeerOz. The discussion is illustrated using UV-Vis spectra collected on acidic Fe(III) solutions containing varying LiCl concentrations, and showing the change from the hexaaquo Fe(H 2O) 63+ complex to the tetrahedral FeCl 4- complex.

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 ...

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.)

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.

Indirect human exposure assessment of airborne lead deposited on soil via a simplified fate and speciation modelling approach.

Science.gov (United States)

Pizzol, Massimo; Bulle, Cécile; Thomsen, Marianne

2012-04-01

In order to estimate the total exposure to the lead emissions from a municipal waste combustion plant in Denmark, the indirect pathway via ingestion of lead deposited on soil has to be quantified. Multi-media fate models developed for both Risk Assessment (RA) and Life Cycle Assessment (LCA) can be used for this purpose, but present high uncertainties in the assessment of metal's fate. More sophisticated and metal-specific geochemical models exist, that could lower the uncertainties by e.g. accounting for metal speciation, but they require a large amount of data and are unpractical to combine broadly with other fate and dispersion models. In this study, a Simplified Fate & Speciation Model (SFSM) is presented, that is based on the parsimony principle: "as simple as possible, as complex as needed", and that can be used for indirect human exposure assessment in different context like RA and regionalized LCA. SFSM couples traditional multi-media mass balances with empirical speciation models in a tool that has a simple theoretical framework and that is not data-intensive. The model calculates total concentration, dissolved concentration, and free ion activity of Cd, Cu, Ni, Pb and Zn in different soil layers, after accounting for metal deposition and dispersion. The model is tested for these five metals by using data from peer reviewed literature. Results show good accordance between measured and calculated values (factor of 3). The model is used to predict the human exposure via soil to lead initially emitted into air by the waste combustion plant and both the lead cumulative exposure and intake fraction are calculated. Copyright © 2012 Elsevier B.V. All rights reserved.

Genome Size, Molecular Phylogeny, and Evolutionary History of the Tribe Aquilarieae (Thymelaeaceae, the Natural Source of Agarwood

Directory of Open Access Journals (Sweden)

Azman H. Farah

2018-05-01

Full Text Available The tribe Aquilarieae of the family Thymelaeaceae consists of two genera, Aquilaria and Gyrinops, with a total of 30 species, distributed from northeast India, through southeast Asia and the south of China, to Papua New Guinea. They are an important botanical resource for fragrant agarwood, a prized product derived from injured or infected stems of these species. The aim of this study was to estimate the genome size of selected Aquilaria species and comprehend the evolutionary history of Aquilarieae speciation through molecular phylogeny. Five non-coding chloroplast DNA regions and a nuclear region were sequenced from 12 Aquilaria and three Gyrinops species. Phylogenetic trees constructed using combined chloroplast DNA sequences revealed relationships of the studied 15 members in Aquilarieae, while nuclear ribosomal DNA internal transcribed spacer (ITS sequences showed a paraphyletic relationship between Aquilaria species from Indochina and Malesian. We exposed, for the first time, the estimated divergence time for Aquilarieae speciation, which was speculated to happen during the Miocene Epoch. The ancestral split and biogeographic pattern of studied species were discussed. Results showed no large variation in the 2C-values for the five Aquilaria species (1.35–2.23 pg. Further investigation into the genome size may provide additional information regarding ancestral traits and its evolution history.

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.

Complexation of Eu(III), Th(IV) and U(VI) by humic substances

International Nuclear Information System (INIS)

Moulin, V.; Reiller, P.; Dautel, C.; Plancque, G.; Laszak, I.; Moulin, C.

1999-01-01

Complexation of actinides by humic substances has been studied by different techniques depending on the actinide and its oxidation state. For trivalent actinide (using a rare earth element, Eu as an analogue of trivalent actinide), Time-Resolved Laser-Induced Fluorescence (TRLIF) has been retained as a method for direction speciation at low level. By varying pH and physicochemical conditions (absence of carbonate ions) and at fixed ionic strength, it is possible together to identify spectrally and temporally, all the hydroxo and carbonato complexes. This approach has also been retained for U(VI) as a model of hexavalent actinide, for which hydroxo complexes have been characterized by TRLIF (the simple carbonato complexes are not fluorescent). In the case of U(VI), titrations hy humic acids of U(VI) solutions at various pH have allowed to characterize organic complexes formed with U(VI): single complexes (UO 2 HA) and mixed complexes (UO 2 (OH) 3 HA). The impact on U(VI) speciation has then been identified. In the case of Th(IV) as a model of tetravalent actinides, a competitive method has been used to obtain data on the Th-HA system by studying the ternary system silica colloid/HA/Th at constant pH (Schubert method). Apparent interaction constants have been calculated depending on Th hydrolysis constants used. A study of the system Th/HA/silica has a function of pH and for different HA concentrations has shown the strong complexing character of humic acids towards Th in the pH range 4-9. (orig.)

Felsenstein's“one-allele model”of speciation: The role of philopatry in the initial stages of host plant mediated reproductive isolation in Enchenopa binotata

Directory of Open Access Journals (Sweden)

Frank W. STEARNS, Kelley J. TILMON, Thomas K. WOOD

2013-10-01

Full Text Available The study of speciation genetics is primarily concerned with identifying the genetic traits that allow divergent selection to overcome the homogenizing effects of gene flow. Felsenstein reviewed this race between gene flow and selection, concluding that speciation with gene flow was unlikely under a “two-allele model” (where two traits were necessary for reproductive isolation but that divergence could occur quite easily under a “one-allele model.” Despite this finding, much of the sympatric speciation research involving phytophagous insects has relied on a two-trait model, where insects evolve both preferences for and increased performance on novel host plants. Philopatry (a tendency to remain where one was born is known to occur in phytophagous insects and is a single trait isolation mechanism. However, it is traditionally invoked as simply augmenting reproductive isolation. Species in the Enchenopa binotata complex are believed to have speciated in sympatry. They exhibit host plant prefe­rences, host specific performance advantages and strong philopatry. We experimentally shifted E. binotata to evolutionarily novel host plants. Previous research has demonstrated that the experimental population of insects possesses genetic variation in prefe­rence and performance to the novel host. The degree of philopatry at mating and egg-laying was assayed for the first four years under full choice conditions. Host plant preference and performance was assayed after eight years. Philopatry was an immediate and strong isolating mechanism, while preference for and performance on the novel host lagged. We therefore suggest that philopatry may be a more important mechanism in the early stages of a host shift than previously believed [Current Zoology 59 (5: 658-666, 2013].

Migration of radiocesium and radioiodine released by FDNPP accident in the terrestrial environment and its interpretation by their speciation analyses

International Nuclear Information System (INIS)

Takahashi, Yoshio; Fan, Qiaohui; Sakaguchi, Aya; Tanaka, Kazuya; Togo, Yoko S.

2013-01-01

Distribution of radiocesium and radioiodine such as vertical profile in soil layer, particulate matter-water distribution in river water, and size distributions in sediments were studied to understand their migration in the terrestrial environment in Fukushima area. In addition, speciation studies on cesium and iodine focusing on (1) the surface complex structure of cesium on clay minerals and (2) formation of organoiodine in soil have been conducted, which can clearly explain the possible chemical processes that control the behavior of these radionuclides in the terrestrial environment. (author)

Influence of natural organic matter and mineral surfaces upon the radionuclide speciation in an environmental context

International Nuclear Information System (INIS)

Janot, N.

2011-01-01

This study deals with interactions occurring in a ternary europium(III)/humic acid(HA)/α-Al 2 O 3 system, depending on solution conditions (pH, ionic strength, organic concentration). These interactions were studied at a macroscopic scale - quantifying Eu(III) and/or HA adsorption onto the mineral surface - and using time-resolved luminescence spectroscopy. The presence of HA modifies Eu(III) behavior toward the mineral surface. Analysis showed a Eu(III)-HA complexation in the ternary system, in all the conditions studied. However, Eu(III) complexation with the mineral surface is occurring at high pH and ionic strength only. Spectrophotometric titrations were validated as a method to study HA reactivity at environmental relevant concentrations. They have been used to determine modifications of HA reactivity after adsorption onto the alumina surface depending on initial HA concentration. These results have then be used to model Eu(III) speciation in the ternary system, using the CD-MUSIC and NICA-Donnan models for mineral and organic complexation, respectively. (author) [fr

Two modified versions of the speciation code PHREEQE for modelling macromolecule-proton/cation interaction

International Nuclear Information System (INIS)

Falck, W.E.

1991-01-01

There is a growing need to consider the influence of organic macromolecules on the speciation of ions in natural waters. It is recognized that a simple discrete ligand approach to the binding of protons/cations to organic macromolecules is not appropriate to represent heterogeneities of binding site distributions. A more realistic approach has been incorporated into the speciation code PHREEQE which retains the discrete ligand approach but modifies the binding intensities using an electrostatic (surface complexation) model. To allow for different conformations of natural organic material two alternative concepts have been incorporated: it is assumed that (a) the organic molecules form rigid, impenetrable spheres, and (b) the organic molecules form flat surfaces. The former concept will be more appropriate for molecules in the smaller size range, while the latter will be more representative for larger size molecules or organic surface coatings. The theoretical concept is discussed and the relevant changes to the standard PHREEQE code are explained. The modified codes are called PHREEQEO-RS and PHREEQEO-FS for the rigid-sphere and flat-surface models respectively. Improved output facilities for data transfer to other computers, e.g. the Macintosh, are introduced. Examples where the model is tested against literature data are shown and practical problems are discussed. Appendices contain listings of the modified subroutines GAMMA and PTOT, an example input file and an example command procedure to run the codes on VAX computers

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)

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

Energy Technology Data Exchange (ETDEWEB)

Attanayake, Chammi P.; Hettiarachchi, Ganga M.; Ma, Qing; Pierzynski, Gary M.; Ransom, Michel D. (NWU); (KSU)

2017-01-01

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

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.

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.

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

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

International Nuclear Information System (INIS)

Choppin, G.; Felmy, A.R.

1997-01-01

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

The Hawaiian cave planthoppers (Homoptera: Fulgoroidea: Cixiidae - A model for rapid subterranean speciation?

Directory of Open Access Journals (Sweden)

Hannelore Hoch

1997-01-01

Full Text Available After the successful colonization of a single ancestral species in the Hawaiian Islands, planthoppers of the cixiid genus Oliarus underwent intensive adaptive radiation resulting in 80 described endemic species. Oliarus habitats range from montaneous rain forests to dry coastal biotopes and subterranean environments. At least 7 independant evolutionary lines represented by different species have adapted to lava tubes on Molokai (1, Maui (3, and Hawaii Island (3. Behavioral and morphological studies on one of these evolutionary lines on Hawaii Island, the blind, flight- and pigmentless Oliarus polyphentus have provided evidence for reproductive isolation between allopatric populations which may in fact be separate species. Significant differences in song parameters were observed even between populations from neighbouring lava tubes, although the planthoppers are capable of underground migration through the voids and cracks of the mesocavernous rock system which is extant in young basalt: after a little more than 20 years, lava tubes within the Mauna Ulu 1974 flow had been colonized by O. ‘polyphenius” individuals, most probably originating from a near-by forestkipuka. Amazingly, this species complex is found on the youngest of the Hawaiian Islands, with probably less than 0.5 m.y., which suggests rapid speciation processes. Field observations have led to the development of a hypothesis to match underground speciation with the dynamics of vegetational succession on the surface of active volcanoes. Planthopper range partitioning and geographic separation of populations by young lava flows, founder events and small population size may be important factors involved in rapid divergence.

Speciation in little: the role of range and body size in the diversification of Malagasy mantellid frogs

Directory of Open Access Journals (Sweden)

Vences Miguel

2011-07-01

Full Text Available Abstract Background The rate and mode of lineage diversification might be shaped by clade-specific traits. In Madagascar, many groups of organisms are characterized by tiny distribution ranges and small body sizes, and this high degree of microendemism and miniaturization parallels a high species diversity in some of these groups. We here investigate the geographic patterns characterizing the radiation of the frog family Mantellidae that is virtually endemic to Madagascar. We integrate a newly reconstructed near-complete species-level timetree of the Mantellidae with georeferenced distribution records and maximum male body size data to infer the influence of these life-history traits on each other and on mantellid diversification. Results We reconstructed a molecular phylogeny based on nuclear and mitochondrial DNA for 257 species and candidate species of the mantellid frog radiation. Based on this phylogeny we identified 53 well-supported pairs of sister species that we used for phylogenetic comparative analyses, along with whole tree-based phylogenetic comparative methods. Sister species within the Mantellidae diverged at 0.2-14.4 million years ago and more recently diverged sister species had geographical range centroids more proximate to each other, independently of their current sympatric or allopatric occurrence. The largest number of sister species pairs had non-overlapping ranges, but several examples of young microendemic sister species occurring in full sympatry suggest the possibility of non-allopatric speciation. Range sizes of species included in the sister species comparisons increased with evolutionary age, as did range size differences between sister species, which rejects peripatric speciation. For the majority of mantellid sister species and the whole mantellid radiation, range and body sizes were associated with each other and small body sizes were linked to higher mitochondrial nucleotide substitution rates and higher clade

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.

Process Description and Operating History for the CPP-601/-640/-627 Fuel Reprocessing Complex at the Idaho National Engineering and Environmental Laboratory

International Nuclear Information System (INIS)

Wagner, E.P.

1999-01-01

The Fuel Reprocessing Complex (FRC) at the Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory was used for reprocessing spent nuclear fuel from the early 1950's until 1992. The reprocessing facilities are now scheduled to be deactivated. As part of the deactivation process, three Resource Conservation and Recovery Act (RCRA) interim status units located in the complex must be closed. This document gathers the historical information necessary to provide a rational basis for the preparation of a comprehensive closure plan. Included are descriptions of process operations and the operating history of the FRC. A set of detailed tables record the service history and present status of the process vessels and transfer lines

Speciation analysis of mercury in sediments, zoobenthos and river water samples by high-performance liquid chromatography hyphenated to atomic fluorescence spectrometry following preconcentration by solid phase extraction

International Nuclear Information System (INIS)

Margetinova, Jana; Houserova-Pelcova, Pavlina; Kuban, Vlastimil

2008-01-01

A high-pressure microwave digestion was applied for microwave-assisted extraction (MAE) of mercury species from sediments and zoobenthos samples. A mixture containing 3 mol L -1 HCl, 50% aqueous methanol and 0.2 mol L -1 citric acid (for masking co-extracted Fe 3+ ) was selected as the most suitable extraction agent. The efficiency of proposed extraction method was better than 95% with R.S.D. below 6%. A preconcentration method utilizing a 'homemade' C18 solid phase extraction (SPE) microcolumns was developed to enhance sensitivity of the mercury species determination using on-column complex formation of mercury-2-mercaptophenol complexes. Methanol was chosen for counter-current elution of the retained mercury complexes achieving a preconcentration factor as much as 1000. The preconcentration method was applied for the speciation analysis of mercury in river water samples. The high-performance liquid chromatography-cold vapour atomic fluorescence spectrometric (HPLC/CV-AFS) method was used for the speciation analysis of mercury. The complete separation of four mercury species was achieved by an isocratic elution of aqueous methanol (65%/35%) on a Zorbax SB-C18 column (4.6 mm x 150 mm, 5 μm) using the same complexation reagent (2-mercaptophenol). The limits of detection were 4.3 μg L -1 for methylmercury (MeHg + ), 1.4 μg L -1 for ethylmercury (EtHg + ), 0.8 μg L -1 for inorganic mercury (Hg 2+ ), 0.8 μg L -1 for phenylmercury (PhHg + )

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.

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.

Response of single bacterial cells to stress gives rise to complex history dependence at the population level

Science.gov (United States)

Mathis, Roland; Ackermann, Martin

2016-01-01

Most bacteria live in ever-changing environments where periods of stress are common. One fundamental question is whether individual bacterial cells have an increased tolerance to stress if they recently have been exposed to lower levels of the same stressor. To address this question, we worked with the bacterium Caulobacter crescentus and asked whether exposure to a moderate concentration of sodium chloride would affect survival during later exposure to a higher concentration. We found that the effects measured at the population level depended in a surprising and complex way on the time interval between the two exposure events: The effect of the first exposure on survival of the second exposure was positive for some time intervals but negative for others. We hypothesized that the complex pattern of history dependence at the population level was a consequence of the responses of individual cells to sodium chloride that we observed: (i) exposure to moderate concentrations of sodium chloride caused delays in cell division and led to cell-cycle synchronization, and (ii) whether a bacterium would survive subsequent exposure to higher concentrations was dependent on the cell-cycle state. Using computational modeling, we demonstrated that indeed the combination of these two effects could explain the complex patterns of history dependence observed at the population level. Our insight into how the behavior of single cells scales up to processes at the population level provides a perspective on how organisms operate in dynamic environments with fluctuating stress exposure. PMID:26960998

Multielement determination and speciation of major-to-ultratrace elements in green tea leaves by ICP-AES and ICP-MS

International Nuclear Information System (INIS)

Matsuura, Hirotaka; Hokura, Akiko; Haraguchi, Hiroki

2000-01-01

In order to investigate the multi-elemental composition of green tea leaves as well as chemical species in tea infusions, inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) were used for elemental analysis and elemental speciation with the aid of size exclusion chromatography (SEC). As a result, the multielement determination of major-to-ultratrace elements in green tea leaves and green tea infusions was carried out by ICP-AES and ICP-MS. About 40 elements in these tea samples could be determined in a wide concentration range of over 8 orders of magnitude. The extraction efficiency of each element was estimated as the ratio of its concentration in tea infusion to that in tea leaves. It was found from the experimental results that the elements in tea leaves could be classified into three characteristic groups, depending on their extraction efficiencies. Furthermore, tea infusions were analyzed by a combined system of SEC, UV absorption detector, and ICP-AES (or ICP-MS) for the speciation of major-to-ultratrace elements. Most of the elements in tea infusions were found to be present as associated complexes with large organic molecules. (author)

Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

International Nuclear Information System (INIS)

Zielińska, Katarzyna; Leeuwen, Herman P. van

2014-01-01

Highlights: • For the first time SPME fiber is coated with polyelectrolyte layer. • Sorption of nanoparticles on the solid phase surface is prevented. • Polyelectrolyte-modified fiber enables extraction of free analyte in presence of sorbing nanoparticles. - Abstract: In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of poly(diallyldimethylammonium chloride), and poly(sodium 4-styrenesulfonate). The modified fiber provides reproducible, convenient and fast extraction capabilities toward the model analyte, triclosan (TCS). A negatively charged polyelectrolyte coating prevents sorbing oxidic nanoparticles from both partitioning into the PDMS phase and aggregation at its surface. The results for the TCS/nanoparticle sample show that the polyelectrolyte layer-modified solid phase extracts just the free form of the organic compound and enables dynamic speciation analysis of the nanoparticulate target analyte complex

X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

International Nuclear Information System (INIS)

Kelly, Shelly D.; Kemner, Kenneth M.; Brooks, Scott C.

2007-01-01

Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations

Anagenetic speciation in Ullung Island, Korea: genetic diversity and structure in the island endemic species, Acer takesimense (Sapindaceae).

Science.gov (United States)

Takayama, Koji; Sun, Byung-Yun; Stuessy, Tod F

2013-05-01

Anagenetic speciation is an important mode of speciation in oceanic islands; one-fourth of the endemic plants are estimated to have been derived via this process. Few studies, however, have critically examined the genetic consequences of anagenesis in comparison with cladogenesis (involved with adaptive radiation). We hypothesize that endemic species originating via anagenetic speciation in a relatively uniform environment should accumulate genetic variation with limited populational differentiation. We undertook a population genetic analysis using nine nuclear microsatellite loci of Acer takesimense, an anagenetically derived species endemic to Ullung Island, Korea, and its continental progenitor A. pseudosieboldianum on the Korean Peninsula. Microsatellite data reveal a clear genetic distinction between the two species. A high F value in the cluster of A. takesimense was found by Bayesian clustering analysis, suggesting a strong episode of genetic drift during colonization and speciation. In comparison with A. pseudosieboldianum, A. takesimense has slightly lower genetic diversity and possesses less than half the number of private and rare alleles. Consistent with predictions, weak geographical genetic structure within the island was found in A. takesimense. These results imply that anagenetic speciation leads to a different pattern of specific and genetic diversity than often seen with cladogenesis.

Unusual conservation of mitochondrial gene order in Crassostrea oysters: evidence for recent speciation in Asia

Science.gov (United States)

2010-01-01

Background Oysters are morphologically plastic and hence difficult subjects for taxonomic and evolutionary studies. It is long been suspected, based on the extraordinary species diversity observed, that Asia Pacific is the epicenter of oyster speciation. To understand the species diversity and its evolutionary history, we collected five Crassostrea species from Asia and sequenced their complete mitochondrial (mt) genomes in addition to two newly released Asian oysters (C. iredalei and Saccostrea mordax) for a comprehensive analysis. Results The six Asian Crassostrea mt genomes ranged from 18,226 to 22,446 bp in size, and all coded for 39 genes (12 proteins, 2 rRNAs and 25 tRNAs) on the same strand. Their genomes contained a split of the rrnL gene and duplication of trnM, trnK and trnQ genes. They shared the same gene order that differed from an Atlantic sister species by as many as nine tRNA changes (6 transpositions and 3 duplications) and even differed significantly from S. mordax in protein-coding genes. Phylogenetic analysis indicates that the six Asian Crassostrea species emerged between 3 and 43 Myr ago, while the Atlantic species evolved 83 Myr ago. Conclusions The complete conservation of gene order in the six Asian Crassostrea species over 43 Myr is highly unusual given the remarkable rate of rearrangements in their sister species and other bivalves. It provides strong evidence for the recent speciation of the six Crassostrea species in Asia. It further indicates that changes in mt gene order may not be strictly a function of time but subject to other constraints that are presently not well understood. PMID:21189147

Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs

KAUST Repository

Yutkin, Maxim P.

2017-08-25

Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water-wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir crude-oil brine/rock (COBR) interfaces. Implementation of LSW in carbonate reservoirs is especially challenging because of high reservoir-brine salinity and, more importantly, because of high reactivity of the rock minerals. Both features complicate understanding of the COBR surface chemistries pertinent to successful LSW. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric carbon dioxide (CO2) and possibly supplemented with additional ionic species, such as sulfates or phosphates. When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that CO2 content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and rock-surface speciation. A simple ion-complexing model predicts the calcite-surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative, depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls the calcite-surface ion-exchange behavior, not the injected-brine composition. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes. Our evaluation of

The Convergence of Ricoeur’s and Von Wright’s Complex Models of History

Directory of Open Access Journals (Sweden)

Linda L. Cox

2014-07-01

Full Text Available The relationship between the structural identity of narrative and the truth claim of the historical narrative work is one of importance to Ricœur. He considers the attempts of two interwoven models of history emerging from analytic philosophy—explanatory and narrative—to articulate this relationship. This paper explores the trajectories of these models as well as the epistemological and ontological crises culminating from the “simple” theses of each model. The solution to these crises requires a more complex method to account for the nature of the connections underlying historical understanding. Georg Henrik von Wright’s provisional or “hybrid” model of explanation and understanding revises the simple explanatory model and is foundational for Ricœur’s own complex revision of narrativist models through his notion of questioning back. The present paper argues that the structure of this hybrid model was unsatisfactory for von Wright, and leads in the direction of Ricœur’s own narrative method. Keywords: Ricœur, von Wright, Narrative, History, Questioning back. Résumé La relation entre l’identité structurale du récit et la prétention à la vérité de l’œuvre de récit historique est fondamentale chez Ricœur. Il considère que les deux modèles historiographiques de provenance analytique – le modèle explicatif et le modèle narratif – peuvent s’articuler. Cet article explore les trajectoires de ces modèles autant que les crises épistémologiques et ontologiques qui culminent dans chacune des thèses prise dans un sens unilatéral. La solution pour remédier à ces crises requiert une méthode plus complexe pour tenir compte de la nature des liens qui sous-tendent la compréhension historique. Le modèle d’explication et de compréhension, provisoire et “hybride,” de Georg Henrik von Wright permet de réviser le simple modèle explicatif. Ceci est fondamental pour comprendre  la révision complexe que

Formation and stability of calcium complexes of dimethyl sulfoxide in water

Czech Academy of Sciences Publication Activity Database

Jakl, M.; Straka, Michal; Jaklová Dytrtová, Jana; Roithová, J.

2014-01-01

Roč. 360, č. 1 (2014), s. 8-14 ISSN 1387-3806 R&D Projects: GA ČR GP13-21409P Grant - others:GA ČR(CZ) GAP206/12/0539 Institutional support: RVO:61388963 Keywords : bonding energies * DFT * ESI-MS * complexation * speciation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

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.

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...

Preconcentration and Speciation of Trace Elements and Trace-Element Analogues of Radionuclides by Neutron Activation Analysis

International Nuclear Information System (INIS)

Chatt, A.

1999-01-01

We have developed a number of preconcentration neutron activation analysis (PNAA) methods in our laboratory for the determination of trace elements in a variety of complex sample matrices. We developed a number of cocrystallization and coprecipitation methods for the determination of trace elements in water samples. We developed several methods for the determination of I in foods and diets. We have developed a number of PNAA methods in our laboratory We determined As and Sb in geological materials and natural waters by coprecipitation with Se and Au in silicate rocks and ores by coprecipitation with Te followed by NAA. We developed an indirect NAA method for the determination of B in leachates of borosilicate glass. We have been interested in studying the speciation of Am, Tc, and Np in simulated vitrified groundwater leachates of high-level wastes under oxid and anoxic conditions using a number of techniques. We then used PNAA methods to study speciation of trace-element analogues of radionuclides. We have been able to apply biochemical techniques and NAA for the separation, preconcentration, and characterization of metalloprotein and protein-bound trace-element species in subcellular fractions of bovine kidneys. Lately, we have concentrated our efforts to develop chemical and biochemical methods in conjunction with NAA, NMR, and MS for the separation and identification of extractable organohalogens (EOX) in tissues of beluga whales, cod, and northern pink shrimp

Complexation of Cu2+, Ni2+ and UO22+ by radiolytic degradation products of bitumen

International Nuclear Information System (INIS)

Loon, L.R. Van; Kopajtic, Z.

1990-05-01

The radiolytic degradation of bitumen was studied under conditions which reflect those which will exist in the near field of a cementitious radioactive waste repository. The potential complexation capacity of the degradation products was studied and complexation experiments with Cu 2+ , Ni 2+ and UO 2 2+ were performed. In general 1:1 complexes with Cu 2+ , Ni 2+ and UO 2 2+ , with log K values of between 5.7 and 6.0 for Cu 2+ , 4.2 for Ni 2+ and 6.1 for UO 2 2+ , were produced at an ionic strength of 0.1 M. The composition of the bitumen water was analysed by GC-MS and IC. The major proportion of the bitumen degradation products in solution were monocarboxylic acids (acetic acid, formic acid, myric acid, stearic acid ...), dicarboxylic acids (oxalic acid, phthalic acid) and carbonates. The experimentally derived log K data are in good agreement with the literature and suggest that oxalate determines the speciation of Cu 2+ , Ni 2+ and UO 2 2+ in the bitumen water below pH=7. However, under the high pH conditions typical of the near field of a cementitious repository, competition with OH-ligands will be large and oxalate, therefore, will not play a significant role in the speciation of radionuclides. The main conclusion of the study is that the radiolytic degradation products of bitumen will have no influence on radionuclide speciation in a cementitious near field and, as such, need not to be considered in the appropriate safety assessment models. (author) 12 figs., 11 tabs., 31 refs

The genetic signature of recent speciation in manta rays (Manta alfredi and M. birostris).